Preliminary theoretical acoustic and rf sounding calculations for MILL RACE

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

Warshaw, S.I.; Dubois, P.F.

1981-11-02

As participant in DOE/ISA's Ionospheric Monitoring Program, LLNL has the responsibility of providing theoretical understanding and calculational support for experimental activities carried out by Los Alamos National Laboratory in using ionospheric sounders to remotely detect violent atmospheric phenomena. We have developed a system of interconnected computer codes which simulate the entire range of atmospheric and ionospheric processes involved in this remote detection procedure. We are able to model the acoustic pulse shape from an atmospheric explosion, the subsequent nonlinear transport of this energy to all parts of the immediate atmosphere including the ionosphere, and the propagation of high-frequency ratio wavesmore » through the acoustically perturbed ionosphere. Los Alamos' coverage of DNA's MILL RACE event provided an excellent opportunity to assess the credibility of the calculational system to correctly predict how ionospheric sounders would respond to a surface-based chemical explosion. In this experiment, 600 tons of high explosive were detonated at White Sands Missile Range at 12:35:40 local time on 16 September 1981. Vertical incidence rf phase sounders and bistatic oblique incidence rf sounders fielded by Los Alamos and SRI International throughout New Mexico and southern Colorado detected the ionospheric perturbation that ensued. A brief account of preliminary calculations of the acoustic disturbance and the predicted ionospheric sounder signatures for MILL RACE is presented. (WHK)« less

A formula for calculating theoretical photoelectron fluxes resulting from the He/+/ 304 A solar spectral line

NASA Technical Reports Server (NTRS)

Richards, P. G.; Torr, D. G.

1981-01-01

A simplified method for the evaluation of theoretical photoelectron fluxes in the upper atmosphere resulting from the solar radiation at 304 A is presented. The calculation is based on considerations of primary and cascade (secondary) photoelectron production in the two-stream model, where photoelectron transport is described by two electron streams, one moving up and one moving down, and of loss rates due to collisions with neutral gases and thermal electrons. The calculation is illustrated for the case of photoelectrons at an energy of 24.5 eV, and it is noted that the 24.5-eV photoelectron flux may be used to monitor variations in the solar 304 A flux. Theoretical calculations based on various ionization and excitation cross sections of Banks et al. (1974) are shown to be in generally good agreement with AE-E measurements taken between 200 and 235 km, however the use of more recent, larger cross sections leads to photoelectron values a factor of two smaller than observations but in agreement with previous calculations. It is concluded that a final resolution of the photoelectron problem may depend on a reevaluation of the inelastic electron collision cross sections.

Number theoretical foundations in cryptography

NASA Astrophysics Data System (ADS)

Atan, Kamel Ariffin Mohd

2017-08-01

In recent times the hazards in relationships among entities in different establishments worldwide have generated exciting developments in cryptography. Central to this is the theory of numbers. This area of mathematics provides very rich source of fundamental materials for constructing secret codes. Some number theoretical concepts that have been very actively used in designing crypto systems will be highlighted in this presentation. This paper will begin with introduction to basic number theoretical concepts which for many years have been thought to have no practical applications. This will include several theoretical assertions that were discovered much earlier in the historical development of number theory. This will be followed by discussion on the "hidden" properties of these assertions that were later exploited by designers of cryptosystems in their quest for developing secret codes. This paper also highlights some earlier and existing cryptosystems and the role played by number theoretical concepts in their constructions. The role played by cryptanalysts in detecting weaknesses in the systems developed by cryptographers concludes this presentation.

Theoretical calculations of positron annihilation characteristics in inorganic solids -- Recent advances and problems

NASA Astrophysics Data System (ADS)

Sob, M.; Sormann, H.; Kuriplach, J.

Principles and applications of positron annihilation spectroscopy to electronic structure and defect studies are briefly reviewed and some recent advances and pending problems are illustrated by specific examples. In particular, it turns out that the sensitivity of calculated momentum densities of electron-positron annihilation pairs (MDAP) to the choice of electron crystal potential is higher or comparable to its sensitivity with respect to the choice of description of the electron-positron interaction. As a result, it is very hard to distinguish between various electron-positron interaction theories on the basis of the comparison of theoretical and experimental MDAPs. Furthermore, the positron affinity is determined theorttically for several systems having a band gap (semiconductors, insulators). It appears that the calculated positron affinities are significantly underestimated when compared to experimental data and, apparently, electron-positron interactions in such systems are not described satisfactorily by contemporary theoretical approaches. The above examples are related rather to electronic structure studies, but positrons are often used to investigate various open-volume defects in solids, which is dealt with in the last illustration. A non-selfconsistent computational technique suitable for the theoretical examination of configurations having large number (thousands) of non-equivalent atoms has been updated recently to treat non-periodic solids. It is based on the superposition of atomic densities in order to approximate the electronic density of the system studied. Though the charge redistribution due to selfconsistency effects is neglected, positron annihilation characteristics are determined quite reasonably. This allows for studying properties of extended defects like grain boundaries (and other interfaces), dislocations, precipitates, etc., which is very helpful when interpreting experimental positron annihilation data. Our technique is

Ethylenediammonium dication: H-bonded complexes with terephthalate, chloroacetate, phosphite, selenite and sulfamate anions. Detailed vibrational spectroscopic and theoretical studies of ethylenediammonium terephthalate

NASA Astrophysics Data System (ADS)

Marchewka, M. K.; Drozd, M.

2012-12-01

Crystalline complexes between ethylenediammonium dication and terephthalate, chloroacetate, phosphite, selenite and sulfamate anions were obtained by slow evaporation from water solution method. Room temperature powder infrared and Raman measurements were carried out. For ethylenediammonium terephthalate theoretical calculations of structure were performed by two ways: ab-initio HF and semiempirical PM3. In this case the PM3 method gave more accurate structure (closer to X-ray results). The additional PM3 calculations of vibrational spectra were performed. On the basis theoretical approach and earlier vibrational studies of similar compounds the vibrational assignments for observed bands have been proposed. All compounds were checked for second harmonic generation (SHG).

Estimation of the Maximum Theoretical Productivity of Fed-Batch Bioreactors

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

Bomble, Yannick J; St. John, Peter C; Crowley, Michael F

2017-10-18

A key step towards the development of an integrated biorefinery is the screening of economically viable processes, which depends sharply on the yields and productivities that can be achieved by an engineered microorganism. In this study, we extend an earlier method which used dynamic optimization to find the maximum theoretical productivity of batch cultures to explicitly include fed-batch bioreactors. In addition to optimizing the intracellular distribution of metabolites between cell growth and product formation, we calculate the optimal control trajectory of feed rate versus time. We further analyze how sensitive the productivity is to substrate uptake and growth parameters.

DFT calculation of pKa’s for dimethoxypyrimidinylsalicylic based herbicides

NASA Astrophysics Data System (ADS)

Delgado, Eduardo J.

2009-03-01

Dimethoxypyrimidinylsalicylic derived compounds show potent herbicidal activity as a result of the inhibition of acetohydroxyacid synthase, the first common enzyme in the biosynthetic pathway of the branched-chain aminoacids (valine, leucine and isoleucine) in plants, bacteria and fungi. Despite its practical importance, this family of compounds have been poorly characterized from a physico-chemical point of view. Thus for instance, their pK a's have not been reported earlier neither experimentally nor theoretically. In this study, the acid-dissociation constants of 39 dimethoxypyrimidinylsalicylic derived herbicides are calculated by DFT methods at B3LYP/6-31G(d,p) level of theory. The calculated values are validated by two checking tests based on the Hammett equation.

Raman and infrared spectra and theoretical calculations of dipicolinic acid, dinicotinic acid, and their dianions

NASA Astrophysics Data System (ADS)

McCann, Kathleen; Laane, Jaan

2008-11-01

The Raman and infrared spectra of dipicolinic acid (DPA) and dinicotinic acid (DNic) and their salts (CaDPA, Na 2DPA, and CaDNic) have been recorded and the spectra have been assigned. Ab initio and DFT calculations were carried out to predict the structures and vibrational spectra and were compared to the experimental results. Because of extensive intermolecular hydrogen bonding in the crystals of these molecules, the calculated structures and spectra for the individual molecules agree only moderately well with the experimental values. Theoretical calculations were also carried out for DPA dimers and DPA·2H 2O to better understand the intermolecular interactions. The spectra do show that DPA and its calcium salt, which are present in anthrax spores, can be distinguished from the very similar DNic and CaDNic.

Theoretical Crystal-Field Calculations for Rare-Earth Ions in III-V semiconductor Compounds

DTIC Science & Technology

1991-10-01

AD-A243 098 TIC HDL-TM-91-16 1 Ii! 1 I!EiIII ’ii F CT F October 1991 aC7 1991J Theoretical Crystal-Field Calculations for Rare-Earth Ions in III-V...0188). Washngton. DC 20503 1 . AGENCY USE ONLY (Leave bia*) 2. REPORT DATE 3. REPORT TYPE AND DATES COVERED October 1991 Summary, from Jan 91 toJul 91...Laboratories HDL-TM-9 1 -16 2800 Powder Mill Road Adelphi, MD 20783-1197 9. SPONSORNG#AONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORINGMONITORING

Ethylenediammonium dication: H-bonded complexes with terephthalate, chloroacetate, phosphite, selenite and sulfamate anions. Detailed vibrational spectroscopic and theoretical studies of ethylenediammonium terephthalate.

PubMed

Marchewka, M K; Drozd, M

2012-12-01

Crystalline complexes between ethylenediammonium dication and terephthalate, chloroacetate, phosphite, selenite and sulfamate anions were obtained by slow evaporation from water solution method. Room temperature powder infrared and Raman measurements were carried out. For ethylenediammonium terephthalate theoretical calculations of structure were performed by two ways: ab-initio HF and semiempirical PM3. In this case the PM3 method gave more accurate structure (closer to X-ray results). The additional PM3 calculations of vibrational spectra were performed. On the basis theoretical approach and earlier vibrational studies of similar compounds the vibrational assignments for observed bands have been proposed. All compounds were checked for second harmonic generation (SHG). Copyright © 2012 Elsevier B.V. All rights reserved.

Using experimental studies and theoretical calculations to analyze the molecular mechanism of coumarin, p-hydroxybenzoic acid, and cinnamic acid

NASA Astrophysics Data System (ADS)

Hsieh, Tiane-Jye; Su, Chia-Ching; Chen, Chung-Yi; Liou, Chyong-Huey; Lu, Li-Hwa

2005-05-01

Three natural products, Coumarin ( 1), p-hydroxybenzoic acid ( 2), trans-cinnamic acid ( 3) were isolated from the natural plant of indigenous cinnamon and the structures including relative stereochemistry were elucidated on the basis of spectroscopic data and theoretical calculations. Their sterochemical structures were determined by NMR spectroscopy, mass spectroscopy, and X-ray crystallography. The p-hydroxybenzoic acid complex with water is reported to show the existence of two hydrogen bonds. The two hydrogen bonds are formed in the water molecule of two hydrogen-accepting oxygen of carbonyl group of the p-hydroxybenzoic acid. The intermolecular interaction two hydrogen bond of the model system of the water- p-hydroxybenzoic acid was investigated. An experimental study and a theoretical analysis using the B3LYP/6-31G* method in the GAUSSIAN-03 package program were conducted on the three natural products. The theoretical results are supplemented by experimental data. Optimal geometric structures of three compounds were also determined. The calculated molecular mechanics compared quite well with those obtained from the experimental data. The ionization potentials, highest occupied molecular orbital energy, lowest unoccupied molecular orbital energy, energy gaps, heat of formation, atomization energies, and vibration frequencies of the compounds were also calculated. The results of the calculations show that three natural products are stable molecules with high reactive and various other physical properties. The study also provided an explicit understanding of the sterochemical structure and thermodynamic properties of the three natural products.

An experimental and theoretical study of molecular structure and vibrational spectra of 2-methylphenyl boronic acid by density functional theory calculations

NASA Astrophysics Data System (ADS)

Hiremath, Sudhir M.; Hiremath, C. S.; Khemalapure, S. S.; Patil, N. R.

2018-05-01

This paper reports the experimental and theoretical study on the structure and vibrations of 2-Methylphenyl boronic acid (2MPBA). The different spectroscopic techniques such as FT-IR (4000-400 cm-1) and FT-Raman (4000-50 cm-1) of the title molecule in the solid phase were recorded. The geometry of the molecule was fully optimized using density functional theory (DFT) (B3LYP) with 6-311++G(d, p) basis set calculations. The vibrational wavenumbers were also corrected with scale factor to take better results for the calculated data. Vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. The calculated wavenumbers showed the best agreement with the experimental results. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.

Advanced ab initio relativistic calculations of transition probabilities for some O I and O III emission lines

NASA Astrophysics Data System (ADS)

Nguyen, T. V. B.; Chantler, C. T.; Lowe, J. A.; Grant, I. P.

2014-06-01

This work presents new ab initio relativistic calculations using the multiconfiguration Dirac-Hartree-Fock method of some O I and O III transition lines detected in B-type and Wolf-Rayet stars. Our results are the first able to be presented in both the length and velocity gauges, with excellent gauge convergence. Compared to previous experimental and theoretical uncertainties of up to 50 per cent, our accuracies appear to be in the range of 0.33-5.60 per cent, with gauge convergence up to 0.6 per cent. Similar impressive convergence of the calculated energies is also shown. Two sets of theoretical computations are compared with earlier tabulated measurements. Excellent agreement is obtained with one set of transitions but an interesting and consistent discrepancy exists between the current work and the prior literature, deserving of future experimental studies.

Experimental measurements with Monte Carlo corrections and theoretical calculations of neutron inelastic scattering cross section of 115In

NASA Astrophysics Data System (ADS)

Wang, Chao; Xiao, Jun; Luo, Xiaobing

2016-10-01

The neutron inelastic scattering cross section of 115In has been measured by the activation technique at neutron energies of 2.95, 3.94, and 5.24 MeV with the neutron capture cross sections of 197Au as an internal standard. The effects of multiple scattering and flux attenuation were corrected using the Monte Carlo code GEANT4. Based on the experimental values, the 115In neutron inelastic scattering cross sections data were theoretically calculated between the 1 and 15 MeV with the TALYS software code, the theoretical results of this study are in reasonable agreement with the available experimental results.

Virtual Manipulative Materials in Secondary Mathematics: A Theoretical Discussion

ERIC Educational Resources Information Center

Namukasa, Immacukate K.; Stanley, Darren; Tuchtie, Martin

2009-01-01

With the increased use of computer manipulatives in teaching there is need for theoretical discussions on the role of manipulatives. This paper reviews theoretical rationales for using manipulatives and illustrates how earlier distinctions of manipulative materials are broadened to include new forms of materials such as virtual manipulatives.…

Evaluation of steam sterilization processes: comparing calculations using temperature data and biointegrator reduction data and calculation of theoretical temperature difference.

PubMed

Lundahl, Gunnel

2007-01-01

When calculating of the physical F121.1 degrees c-value by the equation F121.1 degrees C = t x 10(T-121.1/z the temperature (T), in combination with the z-value, influences the F121.1 degrees c-value exponentially. Because the z-value for spores of Geobacillus stearothermophilus often varies between 6 and 9, the biological F-value (F(Bio) will not always correspond to the F0-value based on temperature records from the sterilization process calculated with a z-value of 10, even if the calibration of both of them are correct. Consequently an error in calibration of thermocouples and difference in z-values influences the F121.1 degrees c-values logarithmically. The paper describes how results from measurements with different z-values can be compared. The first part describes the mathematics of a calculation program, which makes it easily possible to compare F0-values based on temperature records with the F(BIO)-value based on analysis of bioindicators such as glycerin-water-suspension sensors. For biological measurements, a suitable bioindicator with a high D121-value can be used (such a bioindicator can be manufactured as described in the article "A Method of Increasing Test Range and Accuracy of Bioindicators-Geobacillus stearothermophilus Spores"). By the mathematics and calculations described in this macro program it is possible to calculate for every position the theoretical temperature difference (deltaT(th)) needed to explain the difference in results between the thermocouple and the biointegrator. Since the temperature difference is a linear function and constant all over the process this value is an indication of the magnitude of an error. A graph and table from these calculations gives a picture of the run. The second part deals with product characteristics, the sterilization processes, loading patterns. Appropriate safety margins have to be chosen in the development phase of a sterilization process to achieve acceptable safety limits. Case studies are

Theoretical study on Curcumin: A comparison of calculated spectroscopic properties with NMR, UV vis and IR experimental data

NASA Astrophysics Data System (ADS)

Benassi, Rois; Ferrari, Erika; Lazzari, Sandra; Spagnolo, Ferdinando; Saladini, Monica

2008-12-01

The main target of this study is a high-level computational analysis of Curcumin, employing DFT approach with two different sets of basis functions (B3LYP/6-31G ∗ and B3LYP/6-311G ∗∗). Accurate quantum mechanical studies, both in vacuum and in methanol medium, are carried out with the aim to analyze the conformational equilibria, to find the most stable equilibrium structure and to define the nature of the molecular orbitals, fundamental to explain Curcumin binding characteristic. Our theoretical calculations, performed at B3LYP/6-31G ∗ and B3LYP/6-311G ∗∗ levels both in vacuum and in methanol medium, confirm that the keto-enolic forms are more stable than the di-keto one, whose extremely low population suggests that this structure should not influence Curcumin properties. Keto-enolic form C results the most stable, independently on calculation level and solvent (methanol) effect. HOMO and LUMO molecular orbitals are calculated for all the structures with the two sets of basis with very similar results. MEPs show that the negative charge is localized on the oxygen atoms, which, in the keto-enolic forms, point in the same direction enabling metal coordination. NMR, UV-vis and FT-IR experimental data are employed in the comparison with electronic and conformational properties of Curcumin resulting from theoretical calculations. The two different calculation levels (B3LYP/6-31G ∗ and B3LYP/6-311G ∗∗) give very similar results. Good linear correlations between the experimental 1H and 13C NMR chemical shifts ( δexp), in methanol- d4 (MeOD) and DMSO- d6 (DMSO), and calculated magnetic isotropic shielding tensors ( σcalc) are found ( δexp = a · σcalc + b). A good prediction of UV-vis experimental maximum absorption ( λmax) on the basis of conformer populations is obtained. A linear relation with a good correlation coefficient is observed plotting the FT-IR experimental wavenumbers vs . the calculated ones, allowing to predict FT-IR spectra.

Resolving an ostensible inconsistency in calculating the evaporation rate of sessile drops.

PubMed

Chini, S F; Amirfazli, A

2017-05-01

This paper resolves an ostensible inconsistency in the literature in calculating the evaporation rate for sessile drops in a quiescent environment. The earlier models in the literature have shown that adapting the evaporation flux model for a suspended spherical drop to calculate the evaporation rate of a sessile drop needs a correction factor; the correction factor was shown to be a function of the drop contact angle, i.e. f(θ). However, there seemed to be a problem as none of the earlier models explicitly or implicitly mentioned the evaporation flux variations along the surface of a sessile drop. The more recent evaporation models include this variation using an electrostatic analogy, i.e. the Laplace equation (steady-state continuity) in a domain with a known boundary condition value, or known as the Dirichlet problem for Laplace's equation. The challenge is that the calculated evaporation rates using the earlier models seemed to differ from that of the recent models (note both types of models were validated in the literature by experiments). We have reinvestigated the recent models and found that the mathematical simplifications in solving the Dirichlet problem in toroidal coordinates have created the inconsistency. We also proposed a closed form approximation for f(θ) which is valid in a wide range, i.e. 8°≤θ≤131°. Using the proposed model in this study, theoretically, it was shown that the evaporation rate in the CWA (constant wetted area) mode is faster than the evaporation rate in the CCA (constant contact angle) mode for a sessile drop. Copyright © 2016 Elsevier B.V. All rights reserved.

PREFACE: Proceedings of the First International Workshop on the Theoretical Calculation of ELNES and XANES (TEX2008) (Nagoya, Japan, 2-4 July 2008) Proceedings of the First International Workshop on the Theoretical Calculation of ELNES and XANES (TEX2008) (Nagoya, Japan, 2-4 July 2008)

NASA Astrophysics Data System (ADS)

Tanaka, Isao; Mizoguchi, Teruyasu; Yamamoto, Tomoyuki

2009-03-01

Both electron energy loss near edge structure (ELNES) spectroscopy and x-ray absorption near edge structure (XANES) spectroscopy provide information on the local structural and chemical environments of selected elements of interest. Recent technological progress in scanning transmission electron microscopy has enabled ELNES measurements with atomic column spatial resolution. Very dilute concentrations (nanograms per milliliter or ppb level) of dopants can be observed using third-generation synchrotron facilities when x-ray fluorescence is measured with highly efficient detectors. With such technical developments, ELNES and XANES have become established as essential tools in a large number of fields of natural science, including condensed matter physics, chemistry, mineralogy and materials science. In addition to these developments in experimental methodology, notable progress in reproducing spectra using theoretical methods has recently been made. Using first-principles methods, one can analyze and interpret spectra without reference to experiment. This is quite important since we are often interested in the analysis of exotic materials or specific atoms located at lattice discontinuities such as surfaces and interfaces, where appropriate experimental data are difficult to obtain. Using the structures predicted by reliable first-principles calculations, one can calculate theoretical ELNES and XANES spectra without too much difficulty even in such cases. Despite the fact that ELNES and XANES probe the same phenomenon—essentially the electric dipole transition from a core orbital to an unoccupied band—there have not been many opportunities for researchers in the two areas to meet and discuss. Theoretical calculations of ELNES spectra have been mainly confined to the electron microscopy community. On the other hand, the theory of XANES has been developed principally by researchers in the x-ray community. Publications describing the methods have been written more

Calculation of molecular excitation rates

NASA Technical Reports Server (NTRS)

Flynn, George

1993-01-01

State-to-state collisional excitation rates for interstellar molecules observed by radio astronomers continue to be required to interpret observed line intensities in terms of local temperatures and densities. A problem of particular interest is collisional excitation of water which is important for modeling the observed interstellar masers. In earlier work supported by a different NASA Grant, excitation of water in collisions with He atoms was studied; after many years of successively more refined calculations that problem now seems to be well understood, and discrepancies with earlier experimental data for related (pressure broadening) phenomena are believed to reflect experimental errors. Because of interstellar abundances, excitation by H2, the dominant interstellar species, is much more important than excitation by He, although it has been argued that rates for excitation by these are similar. Under the current grant theoretical study of this problem has begun which is greatly complicated by the additional degrees of freedom which must be included both in determining the interaction potential and also in the molecular scattering calculation. We have now computed the interaction forces for nearly a thousand molecular geometries and are close to having an acceptable global fit to these points which is necessary for the molecular dynamics calculations. Also, extensive modifications have been made to the molecular scattering code, MOLSCAT. These included coding the rotational basis sets and coupling matrix elements required for collisions of an asymmetric top with a linear rotor. A new method for numerical solution of the coupled equations has been incorporated. Because of the long-ranged nature of the water-hydrogen interaction it is necessary to integrate the equations to rather large intermolecular separations, and the integration methods previously available in MOLSCAT are not ideal for such cases. However, the method used by Alexander in his HIBRIDON code is

Uncertainties Associated with Theoretically Calculated N2-Broadened Half-Widths of H2O Lines

NASA Technical Reports Server (NTRS)

Ma, Q.; Tipping, R. H.; Gamache, R. R.

2010-01-01

With different choices of the cut-offs used in theoretical calculations, we have carried out extensive numerical calculations of the N2-broadend Lorentzian half-widths of the H2O lines using the modified Robert-Bonamy formalism. Based on these results, we are able to thoroughly check for convergence. We find that, with the low-order cut-offs commonly used in the literature, one is able to obtain converged values only for lines with large half-widths. Conversely, for lines with small half-widths, much higher cut-offs are necessary to guarantee convergence. We also analyse the uncertainties associated with calculated half-widths, and these are correlated as above. In general, the smaller the half-widths, the poorer the convergence and the larger the uncertainty associated with them. For convenience, one can divide all H2O lines into three categories, large, intermediate, and small, according to their half-width values. One can use this division to judge whether the calculated half-widths are converged or not, based on the cut-offs used, and also to estimate how large their uncertainties are. We conclude that with the current Robert- Bonamy formalism, for lines in category lone can achieve the accuracy requirement set by HITRAN, whereas for lines in category 3, it 'is impossible to meet this goal.

Fully ab initio calculation of the resonant one-phonon Raman intensity of graphene

NASA Astrophysics Data System (ADS)

Reichardt, Sven; Wirtz, Ludger

We developed a fully ab initio, many-body perturbation theory approach for the calculation of resonant, one-phonon Raman spectra. Our general approach is applicable to any material and here we present its application to the case of graphene. Our diagrammatic, first-principles approach allows us to go beyond and improve on an earlier theoretical study by Basko, which relied on an analytical calculation in certain limits. We investigate the dependence of the G peak intensity on both the excitation energy and Fermi level. Furthermore, our method allows us to identify the relevant electronic quantum pathways and to demonstrate the importance of the contributions from non-resonant electronic transitions. We also applied our approach to the calculation of the resonant one-phonon Raman spectrum of MoS2, with our results being in good agreement with experimental data. SR acknowledges financial support from the National Research Fund (FNR) Luxembourg.

A theoretical study of perovskite CsXCl3 (X=Pb, Cd) within first principles calculations

NASA Astrophysics Data System (ADS)

Ilyas, Bahaa M.; Elias, Badal H.

2017-04-01

The structural, elastic, electronic, optical acoustic and thermodynamic properties of the cubic perovskite CsPbCl3 and CsCdCl3 unit cell, were studied using an ultra-soft pseudopotential plane wave, the Trouiller-Martins-Functional was utilized to perform these calculations. The study was implemented within both the Local Density Approximation (LDA) and the Generalized Gradient Approximation (GGA). the Generalized Gradient Approximation (GGA) scheme proposed by van Leeuwen-Baerends which is the same as the Perdew-Wang 92 functional have been carried out to preform our calculations. As for the Local Density Approximation (LDA) the Teter-Pade parametrization (4/93) was implemented which is the same as Perdew-Wang that in its turn reproduces the Ceperley-Alder-Functional. The computed GGA/LDA-lattice parameter for both CsCdCl3 and CsPbCl3 is in an exquisite agreement with the experimental and theoretical results. The energy band structure shows that CsCdCl3 is Γ-R indirect band gap insulator, while CsPbCl3 is an insulator with a direct band gap Γ-Γ separating the valence bands from the conduction bands, which shows metallic nature after pressure 30 GPa. A hybridization exists between Pb-p states and Cl-p states for CsPbCl3, and Cd-p states and Cs-p states for the CsCdCl3 in the valence bonding region. Optimization of both cell shape (geometry) volume were investigated as pressure of 0-20 GPa and 0-40 GPa for the CsCdCl3 and CsPbCl3 respectively. The Pressure dependence of cubic perovskite elastic constants, Young modulus, bulk and shear moduli, Lame's constants, elastic anisotropy factor, elastic wave velocities, phonon dispersion, Debye temperature and the density of states of CsXCl3 (X=Pb, Cd) were theoretically calculated and compared with the other available theoretical results. The above elastic constants reveal the fact that both compounds are stable and show nature of ductility. For the optical properties, both the static refractive index and dielectric

A theoretical and practical clarification on the calculation of reflection loss for microwave absorbing materials

NASA Astrophysics Data System (ADS)

Liu, Ying; Zhao, Kun; Drew, Michael G. B.; Liu, Yue

2018-01-01

Reflection loss is usually calculated and reported as a function of the thickness of microwave absorption material. However, misleading results are often obtained since the principles imbedded in the popular methods contradict the fundamental facts that electromagnetic waves cannot be reflected in a uniform material except when there is an interface and that there are important differences between the concepts of characteristic impedance and input impedance. In this paper, these inconsistencies have been analyzed theoretically and corrections provided. The problems with the calculations indicate a gap between the background knowledge of material scientists and microwave engineers and for that reason a concise review of transmission line theory is provided along with the mathematical background needed for a deeper understanding of the theory of reflection loss. The expressions of gradient, divergence, Laplacian, and curl operators in a general orthogonal coordinate system have been presented including the concept of reciprocal vectors. Gauss's and Stokes's theorems have been related to Green's theorem in a novel way.

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

PubMed

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

2014-12-15

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

Earlier Age at Menopause, Work and Tobacco Smoke Exposure

PubMed Central

Fleming, Lora E; Levis, Silvina; LeBlanc, William G; Dietz, Noella A; Arheart, Kristopher L; Wilkinson, James D; Clark, John; Serdar, Berrin; Davila, Evelyn P; Lee, David J

2009-01-01

Objective Earlier age at menopause onset has been associated with increased all cause, cardiovascular, and cancer mortality risks. Risk of earlier age at menopause associated with primary and secondary tobacco smoke exposure was assessed. Design Cross-sectional study using a nationally representative sample of US women. Methods 7596 women participants (representing an estimated 79 million US women) from the National Health and Nutrition Examination Survey III were asked: time since last menstrual period, occupation, and tobacco use (including home and workplace secondhand smoke (SHS) exposure). Blood cotinine and follicle-stimulating hormone (FSH) levels were assessed. Logistic regressions for the odds of earlier age at menopause, stratified on race/ethnicity in women 25-50 years and adjusted for survey design, were controlled for age, BMI, education, tobacco smoke exposure, and occupation. Results Among 5029 US women ≥ 25 years with complete data, earlier age at menopause was found among all smokers, and among service and manufacturing industry sector workers. Among women age 25-50 years, there was an increased risk of earlier age at menopause with both primary smoking and with SHS exposure, particularly among Black women. Conclusions Primary tobacco use and SHS exposure were associated with an increased odds of earlier age at menopause in a representative sample of US women. Earlier age at menopause was found for some women worker groups with greater potential occupational SHS exposure. Thus, control of SHS exposures in the workplace may decrease the risk of mortality and morbidity associated with earlier age at menopause in US women workers. PMID:18626414

Theoretical prediction of the electronic transport properties of the Al-Cu alloys based on the first-principle calculation and Boltzmann transport equation

NASA Astrophysics Data System (ADS)

Choi, Garam; Lee, Won Bo

Metal alloys, especially Al-based, are commonly-used materials for various industrial applications. In this paper, the Al-Cu alloys with varying the Al-Cu ratio were investigated based on the first-principle calculation using density functional theory. And the electronic transport properties of the Al-Cu alloys were carried out using Boltzmann transport theory. From the results, the transport properties decrease with Cu-containing ratio at the temperature from moderate to high, but with non-linearity. It is inferred by various scattering effects from the calculation results with relaxation time approximation. For the Al-Cu alloy system, where it is hard to find the reliable experimental data for various alloys, it supports understanding and expectation for the thermal electrical properties from the theoretical prediction. Theoretical and computational soft matters laboratory.

Theoretical molecular studies of astrophysical interest

NASA Technical Reports Server (NTRS)

Flynn, George

1991-01-01

When work under this grant began in 1974 there was a great need for state-to-state collisional excitation rates for interstellar molecules observed by radio astronomers. These were required to interpret observed line intensities in terms of local temperatures and densities, but, owing to lack of experimental or theoretical values, estimates then being used for this purpose ranged over several orders of magnitude. A problem of particular interest was collisional excitation of formaldehyde; Townes and Cheung had suggested that the relative size of different state-to-state rates (propensity rules) was responsible for the anomalous absorption observed for this species. We believed that numerical molecular scattering techniques (in particular the close coupling or coupled channel method) could be used to obtain accurate results, and that these would be computationally feasible since only a few molecular rotational levels are populated at the low temperatures thought to prevail in the observed regions. Such calculations also require detailed knowledge of the intermolecular forces, but we thought that those could also be obtained with sufficient accuracy by theoretical (quantum chemical) techniques. Others, notably Roy Gordon at Harvard, had made progress in solving the molecular scattering equations, generally using semi-empirical intermolecular potentials. Work done under this grant generalized Gordon's scattering code, and introduced the use of theoretical interaction potentials obtained by solving the molecular Schroedinger equation. Earlier work had considered only the excitation of a diatomic molecule by collisions with an atom, and we extended the formalism to include excitation of more general molecular rotors (e.g., H2CO, NH2, and H2O) and also collisions of two rotors (e.g., H2-H2).

Theoretical calculations on the electron absorption spectra of selected Polycyclic Aromatic Hydrocarbons (PAH) and derivatives

NASA Technical Reports Server (NTRS)

Du, Ping

1993-01-01

As a theoretical component of the joint effort with the laboratory of Dr. Lou Allamandola to search for potential candidates for interstellar organic carbon compound that are responsible for the visible diffuse interstellar absorption bands (DIB's), quantum mechanical calculations were performed on the electron absorption spectra of selected polycyclic aromatic hydrocarbons (PAH) and derivatives. In the completed project, 15 different species of naphthalene, its hydrogen abstraction and addition derivatives, and corresponding cations and anions were studied. Using semiempirical quantum mechanical method INDO/S, the ground electronic state of each species was evaluated with restricted Hartree-Fock scheme and limited configuration interaction. The lowest energy spin state for each species was used for electron absorption calculations. Results indicate that these calculations are accurate enough to reproduce the spectra of naphthalene cation and anion observed in neon matrix. The spectral pattern of the hydrogen abstraction and addition derivatives predicted based on these results indicate that the electron configuration of the pi orbitals of these species is the dominant determinant. A combined list of 19 absorptions calculated from 4500 A to 10,400 A were compiled and suggested as potential candidates that are relevant for the DIB's absorptions. Continued studies on pyrene and derivatives revealed the ground state symmetries and multiplicities of its neutral, anionic, and cationic species. Spectral calculations show that the cation (B(sub 3g)-2) and the anion (A(sub u)-2) are more likely to have low energy absorptions in the regions between 10 kK and 20 kK, similar to naphthalene. These absorptions, together with those to be determined from the hydrogen abstraction and addition derivatives of pyrene, can be used to provide additional candidates and suggest experimental work in the search for interstellar compounds that are responsible for DIB's.

Theoretical DFT study on spectroscopic signature and molecular dynamics of neurotransmitter and effect of hydrogen removal

NASA Astrophysics Data System (ADS)

Mukherjee, V.; Singh, N. P.; Yadav, R. A.

2013-04-01

Vibrational spectroscopic study has been made for the serotonin molecule and its deprotonated form. The Infrared and Raman spectra in optimum geometry of these two molecules are calculated using density functional theorem and the normal modes are assigned using potential energy distributions (PEDs) which are calculated using normal coordinate analysis method. The vibrational frequencies of these two molecules are reported and a comparison has been made. The effect of removal of the hydrogen atom from the serotonin molecule upon its geometry and vibrational frequencies are studied. Electronic structures of these two molecules are also studied using natural bond orbital (NBO) analysis. Theoretical Raman spectrum of serotonin at different exciting laser frequencies and at different temperatures are obtained and the results are discussed. Present study reveals that some wrong assignments had been made for serotonin molecule in earlier study.

Theoretical investigations on molecular structure, vibrational spectra, HOMO, LUMO, NBO analysis and hyperpolarizability calculations of thiophene-2-carbohydrazide.

PubMed

Balachandran, V; Janaki, A; Nataraj, A

2014-01-24

The Fourier-Transform infrared and Fourier-Transform Raman spectra of thiophene-2-carbohydrazide (TCH) was recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1). Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of TCH were carried out by DFT (B3LYP) method with 6-311++G(d,p) as basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. Stability of the molecule arising from hyper conjugative interaction and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV spectrum was measured in different solvent. The energy and oscillator strength are calculated by Time Dependant Density Functional Theory (TD-DFT) results. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. The complete assignments were performed on the basis of the potential energy distribution (PED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method. Finally the theoretical FT-IR, FT-Raman, and UV spectra of the title molecule have also been constructed. Copyright © 2013 Elsevier B.V. All rights reserved.

A Theoretical Trombone

ERIC Educational Resources Information Center

LoPresto, Michael C.

2014-01-01

What follows is a description of a theoretical model designed to calculate the playing frequencies of the musical pitches produced by a trombone. The model is based on quantitative treatments that demonstrate the effects of the flaring bell and cup-shaped mouthpiece sections on these frequencies and can be used to calculate frequencies that…

Theoretical gas to liquid shift of (15)N isotropic nuclear magnetic shielding in nitromethane using ab initio molecular dynamics and GIAO/GIPAW calculations.

PubMed

Gerber, Iann C; Jolibois, Franck

2015-05-14

Chemical shift requires the knowledge of both the sample and a reference magnetic shielding. In few cases as nitrogen (15N), the standard experimental reference corresponds to its liquid phase. Theoretical estimate of NMR magnetic shielding parameters of compounds in their liquid phase is then mandatory but usually replaced by an easily-get gas phase value, forbidding direct comparisons with experiments. We propose here to combine ab initio molecular dynamic simulations with the calculations of magnetic shielding using GIAO approach on extracted cluster's structures from MD. Using several computational strategies, we manage to accurately calculate 15N magnetic shielding of nitromethane in its liquid phase. Theoretical comparison between liquid and gas phase allows us to extrapolate an experimental value for the 15N magnetic shielding of nitromethane in gas phase between -121.8 and -120.8 ppm.

Quantum Mechanical Calculations in Collaborations with Experimental Chemistry: The Theoretical Organic Chemistry Perspective

NASA Astrophysics Data System (ADS)

Nguyen, Quynh Nhu Ngoc

synthesized peptides, dynamic simulations were used to sample a large conformational space, generating diverse conformer libraries. Quantum mechanical calculations were then used to determine the relative energies between the conformers, and to compute theoretical NMR data, which were then compared to the experimental values, to determine the best match conformers. Hydropersulfides are commonly found among many mammalian systems, and has recently gained more interest due to their greater nucleophilicity and reducing capacity compared to the related thiols. A series of quantum mechanical calculations were performed for small sulfur-containing molecules in order to help understand these biological compounds. First part of this chapter explores the basics of chemical properties and reactivity of hydropersulfides. The later sections further discuss the redox component of RSSH in generation of the radical RSS, which was found to be unreactive in the presence of O 2 and NO. Modeling the formation of these natural products in the absence of the enzymes has many of its own limitation, but understanding the inherent reactivity of the substrates could be beneficial to future enzymatic studies. Density functional theory calculations of mechanism of caryolene featured one mechanism with a base-catalyzed deprotonation/reprotonation sequence, while the other higher-energy mechanism involved intramolecular proton transfer and a secondary carbocation minimum. This result suggested the role of the enzyme in helping to avoid the secondary carbocation. Both pathways bypassed the concerted suprafacial/suprafacial [2+2] cycloadditions, which were not in violation of orbital symmetry due to their asynchronicity. Quantum mechanical calculations were used to determine theoretical 1H and 13C chemical shifts, which were then compared to the experimental NMR data to assign relative configurations for isohirsut-1-ene, isohirsut-4-ene, and tsukubadiene, which were previously isolated from engineered

Scientific Knowledge Suppresses but Does Not Supplant Earlier Intuitions

ERIC Educational Resources Information Center

Shtulman, Andrew; Valcarcel, Joshua

2012-01-01

When students learn scientific theories that conflict with their earlier, naive theories, what happens to the earlier theories? Are they overwritten or merely suppressed? We investigated this question by devising and implementing a novel speeded-reasoning task. Adults with many years of science education verified two types of statements as quickly…

Theoretical Calculations for Electron Impact Ionization of Atoms and Molecules

NASA Astrophysics Data System (ADS)

Amami, Sadek Mohamed Fituri

In the last twenty years, significant progress has been made for the theoretical treatment of electron impact ionization (e,2e) of atoms and molecules and, for some cases, very nice agreement between experiment and theory has been achieved. In particular, excellent agreement between theory and experiment and theory has been achieved for ionization of hydrogen and helium. However, agreement between experiment and theory is not nearly as good for ionization of larger atoms and molecules. In the first part of this dissertation, different theoretical approaches will be employed to study the triply differential cross section (TDCS) for low and intermediate energy electron-impact ionization of Neon and Argon for different orbital states. There is a very recent interest in studying ionization of Laser aligned atoms in order to get a better understanding about electron impact ionization of molecules. In the next part of this dissertation, results will be presented for electron-impact ionization of three laser aligned atoms, Mg, Ca, and Na. The comparison between the theory and experiment showed that our three body distorted wave (3DW) model gave excellent agreement with experiment in the scattering plane but very poor agreement perpendicular to the scattering plane. An explanation for this poor agreement out of the scattering plane has been provided by comparing our theoretical results with those of the time depended close coupling (TDCC) model and this explanation is also provided in this dissertation. Recently, significant attention has been directed towards obtaining a better under-standing of electron-impact ionization of molecules which are significantly more challenging than atoms. In the last part of this dissertation, results will be presented for electron-impact ionization of three different molecules (N2 , H2O, and CH4) which have been studied comprehensively using different theoretical approximations for different types of geometries. The published papers in

Theoretical modeling of zircon's crystal morphology according to data of atomistic calculations

NASA Astrophysics Data System (ADS)

Gromalova, Natalia; Nikishaeva, Nadezhda; Eremin, Nikolay

2017-04-01

Zircon is an essential mineral that is used in the U-Pb dating. Moreover, zircon is highly resistant to radioactive exposure. It is of great interest in solving both fundamental and applied problems associated with the isolation of high-level radioactive waste. There is significant progress in forecasting of the most energetically favorable crystal structures at the present time. Unfortunately, the theoretical forecast of crystal morphology at high technological level is under-explored nowadays, though the estimation of crystal equilibrium habit is extremely important in studying the physical and chemical properties of new materials. For the first time, the thesis about relation of the equilibrium shape of a crystal with its crystal structure was put forward in the works by O.Brave. According to it, the idealized habit is determined in the simplest case by a correspondence with the reticular densities Rhkl of individual faces. This approach, along with all subsequent corrections, does not take into account the nature of atoms and the specific features of the chemical bond in crystals. The atomistic calculations of crystal surfaces are commonly performed using the energetic characteristics of faces, namely, the surface energy (Esurf), which is a measure of the thermodynamic stability of the crystal face. The stable crystal faces are characterized by small positive values of Esurf. As we know from our previous research (Gromalova et al.,2015) one of the constitutive factors affecting the value of the surface energy in calculations is a choice of potentials model. In this regard, we studied several sets of parameters of atomistic interatomic potentials optimized previously. As the first test model («Zircon 1») were used sets of interatomic potentials of interaction Zr-O, Si-O and O-O in the form of Buckingham potentials. To improve playback properties of zircon additionally used Morse potential for a couple of Zr-Si, as well as the three-particle angular harmonic

Theoretical relation between halo current-plasma energy displacement/deformation in EAST

NASA Astrophysics Data System (ADS)

Khan, Shahab Ud-Din; Khan, Salah Ud-Din; Song, Yuntao; Dalong, Chen

2018-04-01

In this paper, theoretical model for calculating halo current has been developed. This work attained novelty as no theoretical calculations for halo current has been reported so far. This is the first time to use theoretical approach. The research started by calculating points for plasma energy in terms of poloidal and toroidal magnetic field orientations. While calculating these points, it was extended to calculate halo current and to developed theoretical model. Two cases were considered for analyzing the plasma energy when flows down/upward to the diverter. Poloidal as well as toroidal movement of plasma energy was investigated and mathematical formulations were designed as well. Two conducting points with respect to (R, Z) were calculated for halo current calculations and derivations. However, at first, halo current was established on the outer plate in clockwise direction. The maximum generation of halo current was estimated to be about 0.4 times of the plasma current. A Matlab program has been developed to calculate halo current and plasma energy calculation points. The main objective of the research was to establish theoretical relation with experimental results so as to precautionary evaluate the plasma behavior in any Tokamak.

Theoretical Characterization of Visual Signatures and Calculation of Approximate Global Harmonic Frequency Scaling Factors

NASA Astrophysics Data System (ADS)

Kashinski, D. O.; Nelson, R. G.; Chase, G. M.; di Nallo, O. E.; Byrd, E. F. C.

2016-05-01

We are investigating the accuracy of theoretical models used to predict the visible, ultraviolet, and infrared spectra, as well as other properties, of product materials ejected from the muzzle of currently fielded systems. Recent advances in solid propellants has made the management of muzzle signature (flash) a principle issue in weapons development across the calibers. A priori prediction of the electromagnetic spectra of formulations will allow researchers to tailor blends that yield desired signatures and determine spectrographic detection ranges. Quantum chemistry methods at various levels of sophistication have been employed to optimize molecular geometries, compute unscaled harmonic frequencies, and determine the optical spectra of specific gas-phase species. Electronic excitations are being computed using Time Dependent Density Functional Theory (TD-DFT). Calculation of approximate global harmonic frequency scaling factors for specific DFT functionals is also in progress. A full statistical analysis and reliability assessment of computational results is currently underway. Work supported by the ARL, DoD-HPCMP, and USMA.

Dirac R-matrix calculations of photoionization cross sections of Ni XII and atomic structure data of Ni XIII

NASA Astrophysics Data System (ADS)

Nazir, R. T.; Bari, M. A.; Bilal, M.; Sardar, S.; Nasim, M. H.; Salahuddin, M.

2017-02-01

We performed R-matrix calculations for photoionization cross sections of the two ground state configuration 3s23p5 (^2P^o3/2,1/2) levels and 12 excited states of Ni XII using relativistic Dirac Atomic R-matrix Codes (DARC) across the photon energy range between the ionizations thresholds of the corresponding states and well above the thresholds of the last level of the Ni XIII target ion. Generally, a good agreement is obtained between our results and the earlier theoretical photoionization cross sections. Moreover, we have used two independent fully relativistic GRASP and FAC codes to calculate fine-structure energy levels, wavelengths, oscillator strengths, transitions rates among the lowest 48 levels belonging to the configuration (3s23p4, 3s3p5, 3p6, 3s23p33d) in Ni XIII. Additionally, radiative lifetimes of all the excited states of Ni XIII are presented. Our results of the atomic structure of Ni XIII show good agreement with other theoretical and experimental results available in the literature. A good agreement is found between our calculated lifetimes and the experimental ones. Our present results are useful for plasma diagnostic of fusion and astrophysical plasmas.

Vibrational, structural and electronic properties investigation by DFT calculations and molecular docking studies with DNA topoisomerase II of strychnobrasiline type alkaloids: A theoretical approach for potentially bioactive molecules

NASA Astrophysics Data System (ADS)

Costa, Renyer A.; Oliveira, Kelson M. T.; Costa, Emmanoel Vilaça; Pinheiro, Maria L. B.

2017-10-01

A combined experimental and theoretical DFT study of the structural, vibrational and electronic properties of strychnobrasiline and 12-hydroxy-10,11-dimethoxystrychnobrasiline is presented using the Becke three-parameter Lee-Yang-Parr function (B3LYP) and 6-311G(2d,p) basis set. The theoretical geometry optimization data were compared with the X-ray data for a similar structure in the associated literature, showing close values. The calculated HOMO-LUMO gap values showed that the presence of substituents in the benzene ring influences the quantum properties which are directly related to the reactive properties. Theoretical UV spectra agreed well with the measured experimental data, with bands assigned. In addition, Natural Bond Orbitals (NBOs), Mapped molecular electrostatic potential surface (MEPS) and NLO calculations were also performed at the same theory level. The theoretical vibrational analysis revealed several characteristic vibrations that may be used as a diagnostic tool for other strychnobrasiline type alkaloids, simplifying their identification and structural characterization. Molecular docking calculations with DNA Topoisomerase II-DNA complex showed binding free energies values of -8.0 and -9.5 kcal/mol for strychnobrasiline and 12-hydroxy-10,11-dimethoxystrychnobrasiline respectively, while for amsacrine, used for the treatment of leukemia, the binding free energy ΔG presented a value of -10.0 kcal/mol, suggesting that strychnobrasiline derivative alkaloids might exhibit an antineoplastic activity.

Toward Explaining Earlier Retirement after 1970.

ERIC Educational Resources Information Center

Ippolito, Richard A.

1990-01-01

Rule changes in the social security system and pension plans suggest that labor force participation rates for men aged 55 to 64 fell by 20 percent from 1970 through 1986 because of the increase in social security benefits and a change in private pension rules encouraging earlier retirement. (Author/JOW)

Investigation of attractive and repulsive interactions associated with ketones in supercritical CO2, based on Raman spectroscopy and theoretical calculations.

PubMed

Kajiya, Daisuke; Saitow, Ken-ichi

2013-08-07

Carbonyl compounds are solutes that are highly soluble in supercritical CO2 (scCO2). Their solubility governs the efficiency of chemical reactions, and is significantly increased by changing a chromophore. To effectively use scCO2 as solvent, it is crucial to understand the high solubility of carbonyl compounds, the solvation structure, and the solute-solvent intermolecular interactions. We report Raman spectroscopic data, for three prototypical ketones dissolved in scCO2, and four theoretical analyses. The vibrational Raman spectra of the C=O stretching modes of ketones (acetone, acetophenone, and benzophenone) were measured in scCO2 along the reduced temperature Tr = T∕Tc = 1.02 isotherm as a function of the reduced density ρr = ρ∕ρc in the range 0.05-1.5. The peak frequencies of the C=O stretching modes shifted toward lower energies as the fluid density increased. The density dependence was analyzed by using perturbed hard-sphere theory, and the shift was decomposed into attractive and repulsive energy components. The attractive energy between the ketones and CO2 was up to nine times higher than the repulsive energy, and its magnitude increased in the following order: acetone < acetophenone < benzophenone. The Mulliken charges of the three solutes and CO2 molecules obtained by using quantum chemistry calculations described the order of the magnitude of the attractive energy and optimized the relative configuration between each solute and CO2. According to theoretical calculations for the dispersion energy, the dipole-induced-dipole interaction energy, and the frequency shift due to their interactions, the experimentally determined attractive energy differences in the three solutes were attributed to the dispersion energies that depended on a chromophore attached to the carbonyl groups. It was found that the major intermolecular interaction with the attractive shift varied from dipole-induced dipole to dispersion depending on the chromophore in the ketones

Application of the finite-field coupled-cluster method to calculate molecular properties relevant to electron electric-dipole-moment searches

NASA Astrophysics Data System (ADS)

Abe, M.; Prasannaa, V. S.; Das, B. P.

2018-03-01

Heavy polar diatomic molecules are currently among the most promising probes of fundamental physics. Constraining the electric dipole moment of the electron (e EDM ), in order to explore physics beyond the standard model, requires a synergy of molecular experiment and theory. Recent advances in experiment in this field have motivated us to implement a finite-field coupled-cluster (FFCC) approach. This work has distinct advantages over the theoretical methods that we had used earlier in the analysis of e EDM searches. We used relativistic FFCC to calculate molecular properties of interest to e EDM experiments, that is, the effective electric field (Eeff) and the permanent electric dipole moment (PDM). We theoretically determine these quantities for the alkaline-earth monofluorides (AEMs), the mercury monohalides (Hg X ), and PbF. The latter two systems, as well as BaF from the AEMs, are of interest to e EDM searches. We also report the calculation of the properties using a relativistic finite-field coupled-cluster approach with single, double, and partial triples' excitations, which is considered to be the gold standard of electronic structure calculations. We also present a detailed error estimate, including errors that stem from our choice of basis sets, and higher-order correlation effects.

A theoretical trombone

NASA Astrophysics Data System (ADS)

LoPresto, Michael C.

2014-09-01

What follows is a description of a theoretical model designed to calculate the playing frequencies of the musical pitches produced by a trombone. The model is based on quantitative treatments that demonstrate the effects of the flaring bell and cup-shaped mouthpiece sections on these frequencies and can be used to calculate frequencies that compare well to both the desired frequencies of the musical pitches and those actually played on a real trombone.

Ab initio calculation of reaction energies. III. Basis set dependence of relative energies on the FH2 and H2CO potential energy surfaces

NASA Astrophysics Data System (ADS)

Frisch, Michael J.; Binkley, J. Stephen; Schaefer, Henry F., III

1984-08-01

The relative energies of the stationary points on the FH2 and H2CO nuclear potential energy surfaces relevant to the hydrogen atom abstraction, H2 elimination and 1,2-hydrogen shift reactions have been examined using fourth-order Møller-Plesset perturbation theory and a variety of basis sets. The theoretical absolute zero activation energy for the F+H2→FH+H reaction is in better agreement with experiment than previous theoretical studies, and part of the disagreement between earlier theoretical calculations and experiment is found to result from the use of assumed rather than calculated zero-point vibrational energies. The fourth-order reaction energy for the elimination of hydrogen from formaldehyde is within 2 kcal mol-1 of the experimental value using the largest basis set considered. The qualitative features of the H2CO surface are unchanged by expansion of the basis set beyond the polarized triple-zeta level, but diffuse functions and several sets of polarization functions are found to be necessary for quantitative accuracy in predicted reaction and activation energies. Basis sets and levels of perturbation theory which represent good compromises between computational efficiency and accuracy are recommended.

Antileishmanial activity study and theoretical calculations for 4-amino-1,2,4-triazole derivatives

NASA Astrophysics Data System (ADS)

Süleymanoğlu, Nevin; Ünver, Yasemin; Ustabaş, Reşat; Direkel, Şahin; Alpaslan, Gökhan

2017-09-01

4-amino-1,2,4-triazole derivatives; 4-amino-1-((5-mercapto-1,3,4-oxadiazole-2-yl)methyl)-3-(thiophene-2-ylmethyl)-1H-1,2,4-triazole-5(4H)-one (1) and 4-amino-1-((4-amino-5 mercapto-4H-1,2,4-triazole-3-yl)methyl)-3-(thiophene-2-ylmethyl)-1H-1,2,4-triazole-5(4H)-one (2) were studied theoretically by Density Functional Theory (DFT) method with 6-311++G(d,p) basis set, structural and some spectroscopic parameters were determined. Significant differences between the experimental and calculated values of vibrational frequencies and chemical shifts were explained by the presence of intermolecular (Ssbnd H⋯O and Ssbnd H⋯N type) hydrogen bonds in structures. The Molecular Electrostatic Potential (MEP) maps obtained at B3LYP/6-311G++(d,p) support the existence of hydrogen bonds. Compounds were tested against to Leishmania infantum promastigots by microdilution broth assay with Alamar Blue Dye. Antileishmanial activity of 4-amino-1,2,4-triazole derivative (2) is remarkable.

Postseismic viscoelastic surface deformation and stress. Part 1: Theoretical considerations, displacement and strain calculations

NASA Technical Reports Server (NTRS)

Cohen, S. C.

1979-01-01

A model of viscoelastic deformations associated with earthquakes is presented. A strike-slip fault is represented by a rectangular dislocation in a viscoelastic layer (lithosphere) lying over a viscoelastic half-space (asthenosphere). Deformations occur on three time scales. The initial response is governed by the instantaneous elastic properties of the earth. A slower response is associated with viscoelastic relaxation of the lithosphere and a yet slower response is due to viscoelastic relaxation of the asthenosphere. The major conceptual contribution is the inclusion of lithospheric viscoelastic properties into a dislocation model of earthquake related deformations and stresses. Numerical calculations using typical fault parameters reveal that the postseismic displacements and strains are small compared to the coseismic ones near the fault, but become significant further away. Moreover, the directional sense of the deformations attributable to the elastic response, the lithospheric viscoelastic softening, and the asthenospheric viscoelastic flow may differ and depend on location and model details. The results and theoretical arguments suggest that the stress changes accompanying lithospheric relaxation may also be in a different sense than and be larger than the strain changes.

Conformational equilibrium and hydrogen bonding in liquid 2-phenylethylamine explored by Raman spectroscopy and theoretical calculations.

PubMed

Xie, Min; Qi, Yajing; Hu, Yongjun

2011-04-14

2-Phenylethylamine (PEA) is the simplest aromatic amine neurotransmitter, as well as one of the most important. In this work, the conformational equilibrium and hydrogen bonding in liquid PEA were studied by means of Raman spectroscopy and theoretical calculations (DFT/MP2). By changing the orientation of the ethyl and the NH(2) group, nine possible conformers of PEA were found, including four degenerate conformers. Comparison of the experimental Raman spectra of liquid PEA and the calculated Raman spectra of the five typical conformers in selected regions (550-800 and 1250-1500 cm(-1)) revealed that the five conformers can coexist in conformational equilibrium in the liquid. The NH(2) stretching mode of the liquid is red-shifted by ca. 30 cm(-1) relative to that of an isolated PEA molecule (measured previously), implying that intermolecular N-H···N hydrogen bonds play an important role in liquid PEA. The relative intensity of the Raman band at 762 cm(-1) was found to increase with increasing temperature, indicating that the anti conformer might be favorable in liquid PEA at room temperature. The blue shift of the band for the bonded N-H stretch with increasing temperature also provides evidence of the existence of intermolecular N-H···N hydrogen bonds.

Sibutramine characterization and solubility, a theoretical study

NASA Astrophysics Data System (ADS)

Aceves-Hernández, Juan M.; Nicolás Vázquez, Inés; Hinojosa-Torres, Jaime; Penieres Carrillo, Guillermo; Arroyo Razo, Gabriel; Miranda Ruvalcaba, René

2013-04-01

Solubility data from sibutramine (SBA) in a family of alcohols were obtained at different temperatures. Sibutramine was characterized by using thermal analysis and X-ray diffraction technique. Solubility data were obtained by the saturation method. The van't Hoff equation was used to obtain the theoretical solubility values and the ideal solvent activity coefficient. No polymorphic phenomena were found from the X-ray diffraction analysis, even though this compound is a racemic mixture of (+) and (-) enantiomers. Theoretical calculations showed that the polarisable continuum model was able to reproduce the solubility and stability of sibutramine molecule in gas phase, water and a family of alcohols at B3LYP/6-311++G (d,p) level of theory. Dielectric constant, dipolar moment and solubility in water values as physical parameters were used in those theoretical calculations for explaining that behavior. Experimental and theoretical results were compared and good agreement was obtained. Sibutramine solubility increased from methanol to 1-octanol in theoretical and experimental results.

Experimental and theoretical calculation studies on the structure elucidation and absolute configuration of calyxins from Alpinia katsumadai.

PubMed

Wang, Xiao-Bing; Yang, Chang-Shui; Luo, Jian-Guang; Zhang, Chao; Luo, Jun; Yang, Ming-Hua; Kong, Ling-Yi

2017-06-01

Six novel calyxins, named calyxin T-W, ent-calyxin T and ent-calyxin U were isolated from the seeds of Alpinia katsumadai Hayata. Their relative configurations were elucidated by means of detailed UV, IR, NMR and MS spectroscopic data. Their absolute configurations were assigned by collaborative studies on single crystal X-ray diffraction analysis, Mosher's method, electronic circular dichroism (ECD), optical rotation and theoretical calculations. These compounds are Friedel-Cranft alkylation adducts composed of coexisted diarylheptanoids and flavanone from the seeds of Alpinia katsumadai. The antiproliferative activity of the six compounds against NCI-H460, HeLa, SMMC-7721 and HCT-116 cell lines was also reported, and most of them showed moderate to strong activities. Copyright © 2017. Published by Elsevier B.V.

A short history of nomograms and tables used for thermal radiation calculations

NASA Astrophysics Data System (ADS)

Stewart, Seán. M.; Johnson, R. Barry

2016-09-01

The theoretical concept of a perfect thermal radiator, the blackbody, was first introduced by the German physicist Gustav Robert Kirchhoff in 1860. By the latter half of the nineteenth century it had become the object of intense theoretical and experimental investigation. While an attempt at trying to theoretically understand the behavior of radiation emitted from a blackbody was undertaken by many eminent physicists of the day, its solution was not found until 1900 when Max Planck put forward his now famous law for thermal radiation. Today, of course, understanding blackbody behavior is vitally important to many fields including infrared systems, illumination, pyrometry, spectroscopy, astronomy, thermal engineering, cryogenics, and meteorology. Mathematically, the form Planck's law takes is rather cumbersome meaning calculations made with it before the advent of modern computers were rather tedious, dramatically slowing the process of computation. Fortunately, during those early days of the twentieth century researchers quickly realized Planck's equation, and the various functions closely related to it, readily lend themselves to being given a graphical, mechanical, or numerically tabulated form for their evaluation. The first of these computational aids to appear were tables. These arose shortly after Planck introduced his equation, were produced in the greatest number, and remained unsurpassed in their level of accuracy compared to all other aids made. It was also not long before nomograms designed to aid thermal radiation calculations appeared. Essentially a printed chart and requiring nothing more than a straightedge to use, nomograms were cheap and extremely easy to use. Facilitating instant answers to a range of quantities relating to thermal radiation, a number were produced and the inventiveness displayed in some was quite remarkable. In this paper we consider the historical development of many of the nomograms and tables developed and used by generations

Temperature-dependent rate coefficients and theoretical calculations for the OH+Cl2O reaction.

PubMed

Riffault, Véronique; Clark, Jared M; Hansen, Jaron C; Ravishankara, A R; Burkholder, James B

2010-12-17

Rate coefficients k for the OH+Cl(2)O reaction are measured as a function of temperature (230-370 K) and pressure by using pulsed laser photolysis to produce OH radicals and laser-induced fluorescence to monitor their loss under pseudo-first-order conditions in OH. The reaction rate coefficient is found to be independent of pressure, within the precision of our measurements at 30-100 Torr (He) and 100 Torr (N(2)). The rate coefficients obtained at 100 Torr (He) showed a negative temperature dependence with a weak non-Arrhenius behavior. A room-temperature rate coefficient of k(1)(297 K)=(7.5±1.1)×10(-12) cm(3) molecule(-1) s(-1) is obtained, where the quoted uncertainties are 2σ and include estimated systematic errors. Theoretical methods are used to examine OH···OCl(2) and OH···ClOCl adduct formation and the potential-energy surfaces leading to the HOCl+ClO (1a) and Cl+HOOCl (1d) products in reaction (1) at the hybrid density functional UMPW1K/6-311++G(2df,p) level of theory. The OH···OCl(2) and OH···ClOCl adducts are found to have binding energies of about 0.2 kcal mol(-1). The reaction is calculated to proceed through weak pre-reactive complexes. Transition-state energies for channels (1a) and (1d) are calculated to be about 1.4 and about 3.3 kcal mol(-1) above the energy of the reactants. The results from the present study are compared with previously reported rate coefficients, and the interpretation of the possible non-Arrhenius behavior is discussed.

Fesbnd X (X = B, N) binary compounds: First-principles calculations of electronic structures, theoretic hardness and magnetic properties

NASA Astrophysics Data System (ADS)

Hui, Liangliang; Xie, Zhongjing; Li, Chunmei; Chen, Zhi-Qian

2018-04-01

The first-principles calculations are implemented to investigate the electronic structures, theoretic hardness and magnetic properties of iron borides and nitrides with four different crystal systems containing hexagonal (FeB2, ε-Fe3N), tetragonal (Fe2B, α″-Fe16N2), orthorhombic (α-FeB, θ-Fe3B, ζ-Fe2N), and cubic (zb-FeN, rs-FeN, γ‧-Fe4N, γ-Fe23B6) phase. The calculated lattice parameters using RPBE meet well with the experimental results. The cohesive energy and formation enthalpy values indicate the Fesbnd X (X = B, N) binary compounds are thermodynamically stable. Meanwhile, the h-FeB2 is most difficult phase for experimental synthesis among these interstitial compounds. Moreover, magnetic properties are discussed and show that the mean magnetic moments of o-Fe3B and c-Fe23B6 with the values of 2.227 μB and 2.256 μB per iron atom are approaching to that of pure iron (2.32 μB) while the c-Fe4N and t-Fe16N2 with the values of 2.51 and 2.48 μB are beyond that of pure α-Fe. The c-FeN phase shows nonmagnetic in zb-style while rs-type shows antiferromagnetic with a value of 2.52 μB. Furthermore, the average bonding length and Mulliken population combined with electronic structures are also analysed in this paper which provide that strong Fesbnd X and Xsbnd X covalent bonds are responsible for high hardness. Finally, the theoretic hardness of Xsbnd X, Fesbnd X and Fesbnd Fe bonds is predicted by semi empirical hardness theory.

PCM/TD-DFT analysis of 1-bromo-2,3-dichlorobenzene--a combined study of experimental (FT-IR and FT-Raman) and theoretical calculations.

PubMed

Arivazhagan, M; Muniappan, P; Meenakshi, R; Rajavel, G

2013-03-15

This study represents an integral approach towards understanding the electronic and structural aspects of 1-bromo-2,3-dichlorobenzene (BDCB). The experimental spectral bands were structurally assigned with the theoretical calculation, and the thermodynamic properties of the studied compound were obtained from the theoretically calculated frequencies. The relationship between the structure and absorption spectrum and effects of solvents have been discussed. It turns that the hybrid PBE1PBE functional with 6-311+G(d,p) basis provide reliable λ(max) when solvent effects are included in the model. The NBO analysis reveals that the studied compound presents a structural characteristic of electron-transfer within the compound. The frontier molecular orbitals (HOMO-LUMO) are responsible for the electron polarization and electron-transfer properties. The reactivity sites are identified by mapping the electron density into electrostatic potential surface (MESP). Besides, (13)C and (1)H have been calculated using the gauge-invariant atomic orbital (GIAO) method. The thermodynamic properties at different temperatures were calculated, revealing the correlations between standard heat capacity, standard entropy, standard enthalpy changes and temperatures. Furthermore, the studied compound can be used as a good nonlinear optical material due to the higher value of first hyper polarizability (5.7 times greater than that of urea (0.37289×10(-30) esu)). Finally, it is worth to mentioning that solvent induces a considerable red shift of the absorption maximum going from the gas phase, and a slight blue shift of the transition S(0)→S(1) going from less polar to more polar solvents. Copyright © 2012 Elsevier B.V. All rights reserved.

Theoretical characterization of the potential energy surface for NH + NO

NASA Technical Reports Server (NTRS)

Walch, Stephen P.

1992-01-01

The potential energy surface (PES) for NH + NO was characterized using complete active space self-consistent field (CASSCF) gradient calculations to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration interaction (CCI) calculations to refine the energetics. The present results are in qualitative accord with the BAC-MP4 calculations, but there are differences as large as 8 kcal/mol in the detailed energetics. Addition of NH to NO on a (2)A' surface, which correlated with N2 + OH or H + N2O products, involves barriers of 3.2 kcal/mol (trans) and 6.3 kcal/mol (cis). Experimental evidence for these barriers is found in earlier works. The (2)A' surface has no barrier to addition, but does not correlate with products. Surface crossings between the barrierless (2)A' surface and the (2)A' surface may be important. Production of N2 + OH products is predicted to occur via a planar saddle point of (2)A' symmetry. This is in accord with the preferential formation of II(A') lambda doublet levels of OH in earlier experiments. Addition of NH (1)delta to NO is found to occur on an excited state surface and is predicted to lead to N2O product as observed in earlier works.

Full-dimensional quantum calculations of the vibrational states of H5(+).

PubMed

Song, Hongwei; Lee, Soo-Ying; Yang, Minghui; Lu, Yunpeng

2013-03-28

Full-dimensional quantum calculations of the vibrational states of H5(+) have been performed on the accurate potential energy surface developed by Xie et al. [J. Chem. Phys. 122, 224307 (2005)]. The zero point energies of H5(+), H4D(+), D4H(+), and D5(+) and their ground-state geometries are presented and compared with earlier theoretical results. The first 10 low-lying excited states of H5(+) are assigned to the fundamental, overtone, and combination of the H2-H3(+) stretch, the shared proton hopping and the out-of-plane torsion. The ground-state torsional tunneling splitting, the fundamental of the photon hopping mode and the first overtone of the torsion mode are 87.3 cm(-1), 354.4 cm(-1), and 444.0 cm(-1), respectively. All of these values agree well with the diffusion Monte Carlo and multi-configuration time-dependent Hartree results where available.

New strings for old Veneziano amplitudes. II. Group-theoretic treatment

NASA Astrophysics Data System (ADS)

Kholodenko, A. L.

2006-09-01

In this part of our four parts work we use theory of polynomial invariants of finite pseudo-reflection groups in order to reconstruct both the Veneziano and Veneziano-like (tachyon-free) amplitudes and the generating function reproducing these amplitudes. We demonstrate that such generating function and amplitudes associated with it can be recovered with help of finite dimensional exactly solvableN=2 supersymmetric quantum mechanical model known earlier from works of Witten, Stone and others. Using the Lefschetz isomorphism theorem we replace traditional supersymmetric calculations by the group-theoretic thus solving the Veneziano model exactly using standard methods of representation theory. Mathematical correctness of our arguments relies on important theorems by Shepard and Todd, Serre and Solomon proven respectively in the early 50s and 60s and documented in the monograph by Bourbaki. Based on these theorems, we explain why the developed formalism leaves all known results of conformal field theories unchanged. We also explain why these theorems impose stringent requirements connecting analytical properties of scattering amplitudes with symmetries of space-time in which such amplitudes act.

Theoretical and experimental studies of reentry plasmas

NASA Technical Reports Server (NTRS)

Dunn, M. G.; Kang, S.

1973-01-01

A viscous shock-layer analysis was developed and used to calculate nonequilibrium-flow species distributions in the plasma layer of the RAM vehicle. The theoretical electron-density results obtained are in good agreement with those measured in flight. A circular-aperture flush-mounted antenna was used to obtain a comparison between theoretical and experimental antenna admittance in the presence of ionized boundary layers of low collision frequency. The electron-temperature and electron-density distributions in the boundary layer were independently measured. The antenna admittance was measured using a four-probe microwave reflectometer and these measured values were found to be in good agreement with those predicted. Measurements were also performed with another type of circular-aperture antenna and good agreement was obtained between the calculations and the experimental results. A theoretical analysis has been completed which permits calculation of the nonequilibrium, viscous shock-layer flow field for a sphere-cone body. Results are presented for two different bodies at several different altitudes illustrating the influences of bluntness and chemical nonequilibrium on several gas dynamic parameters of interest. Plane-wave transmission coefficients were calculated for an approximate space-shuttle body using a typical trajectory.

Theoretical dissociation energies for ionic molecules

NASA Technical Reports Server (NTRS)

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

1986-01-01

Ab initio calculations at the self-consistent-field and singles plus doubles configuration-interaction level are used to determine accurate spectroscopic parameters for most of the alkali and alkaline-earth fluorides, chlorides, oxides, sulfides, hydroxides, and isocyanides. Numerical Hartree-Fock (NHF) calculations are performed on selected systems to ensure that the extended Slater basis sets employed for the diatomic systems are near the Hartree-Fock limit. Extended Gaussian basis sets of at least triple-zeta plus double polarization equality are employed for the triatomic system. With this model, correlation effects are relatively small, but invariably increase the theoretical dissociation energies. The importance of correlating the electrons on both the anion and the metal is discussed. The theoretical dissociation energies are critically compared with the literature to rule out disparate experimental values. Theoretical (sup 2)Pi - (sup 2)Sigma (sup +) energy separations are presented for the alkali oxides and sulfides.

Theoretical calculation of pKa reveals an important role of Arg205 in the activity and stability of Streptomyces sp. N174 chitosanase.

PubMed

Fukamizo, T; Juffer, A H; Vogel, H J; Honda, Y; Tremblay, H; Boucher, I; Neugebauer, W A; Brzezinski, R

2000-08-18

Based on the crystal structure of chitosanase from Streptomyces sp. N174, we have calculated theoretical pK(a) values of the ionizable groups of this protein using a combination of the boundary element method and continuum electrostatics. The pK(a) value obtained for Arg(205), which is located in the catalytic cleft, was abnormally high (>20.0), indicating that the guanidyl group may interact strongly with nearby charges. Chitosanases possessing mutations in this position (R205A, R205H, and R205Y), produced by Streptomyces lividans expression system, were found to have less than 0.3% of the activity of the wild type enzyme and to possess thermal stabilities 4-5 kcal/mol lower than that of the wild type protein. In the crystal structure, the Arg(205) side chain is in close proximity to the Asp(145) side chain (theoretical pK(a), -1.6), which is in turn close to the Arg(190) side chain (theoretical pK(a), 17.7). These theoretical pK(a) values are abnormal, suggesting that both of these residues may participate in the Arg(205) interaction network. Activity and stability experiments using Asp(145)- and Arg(190)-mutated chitosanases (D145A and R190A) provide experimental data supporting the hypothesis derived from the theoretical pK(a) data and prompt the conclusion that Arg(205) forms a strong interaction network with Asp(145) and Arg(190) that stabilizes the catalytic cleft.

Excited State Charge Transfer reaction with dual emission from 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile: Spectral measurement and theoretical density functional theory calculation

NASA Astrophysics Data System (ADS)

Jana, Sankar; Dalapati, Sasanka; Ghosh, Shalini; Kar, Samiran; Guchhait, Nikhil

2011-07-01

The excited state intramolecular charge transfer process in donor-chromophore-acceptor system 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile (DMAPPDN) has been investigated by steady state absorption and emission spectroscopy in combination with Density Functional Theory (DFT) calculations. This flexible donor acceptor molecule DMAPPDN shows dual fluorescence corresponding to emission from locally excited and charge transfer state in polar solvent. Large solvatochromic emission shift, effect of variation of pH and HOMO-LUMO molecular orbital pictures support excited state intramolecular charge transfer process. The experimental findings have been correlated with the calculated structure and potential energy surfaces based on the Twisted Intramolecular Charge Transfer (TICT) model obtained at DFT level using B3LYP functional and 6-31+G( d, p) basis set. The theoretical potential energy surfaces for the excited states have been generated in vacuo and acetonitrile solvent using Time Dependent Density Functional Theory (TDDFT) and Time Dependent Density Functional Theory Polarized Continuum Model (TDDFT-PCM) method, respectively. All the theoretical results show well agreement with the experimental observations.

Theoretical calculation of coherent Laue-case conversion between x-rays and ALPs for an x-ray light-shining-through-a-wall experiment

NASA Astrophysics Data System (ADS)

Yamaji, T.; Yamazaki, T.; Tamasaku, K.; Namba, T.

2017-12-01

Single crystals have high atomic electric fields as much as 1 011 V /m , which correspond to magnetic fields of ˜103 T . These fields can be utilized to convert x-rays into axionlike particles (ALPs) coherently similar to x-ray diffraction. In this paper, we perform the first theoretical calculation of the Laue-case conversion in crystals based on the Darwin dynamical theory of x-ray diffraction. The calculation shows that the Laue-case conversion has longer interaction length than the Bragg case, and that ALPs in the keV range can be resonantly converted by tuning an incident angle of x-rays. ALPs with mass up to O (10 keV ) can be searched by light-shining-through-a-wall (LSW) experiments at synchrotron x-ray facilities.

Research promises earlier warning for grapevine canker diseases

USDA-ARS?s Scientific Manuscript database

When it comes to detecting and treating vineyards for grapevine canker diseases (also called trunk diseases), like Botryosphaeria dieback (Bot canker), Esca, Eutypa dieback and Phomopsis dieback, the earlier the better, says plant pathologist Kendra Baumgartner, with the USDA’s Agricultural Research...

An earlier de motu cordis.

PubMed Central

Daly, Walter J.

2004-01-01

Thirteenth century medical science, like medieval scholarship in general, was directed at reconciliation of Greek philosophy/science with prevailing medieval theology and philosophy. Peter of Spain [later Pope John XXI] was the leading medical scholar of his time. Peter wrote a long book on the soul. Imbedded in it was a chapter on the motion of the heart. Peter's De Motu was based on his own medical experience and Galen's De Usu Partium and De Usu Respirationis and De Usu Pulsuum. This earlier De Motu defines a point on the continuum of intellectual development leading to us and into the future. Thirteenth century scholarship relied on past authority to a degree that continues to puzzle and beg explanation. Images Fig. 1 PMID:17060956

Synthesis, crystal structure, vibrational spectra and theoretical calculations of quantum chemistry of a potential antimicrobial Meldrum's acid derivative

NASA Astrophysics Data System (ADS)

Campelo, M. J. M.; Freire, P. T. C.; Mendes Filho, J.; de Toledo, T. A.; Teixeira, A. M. R.; da Silva, L. E.; Bento, R. R. F.; Faria, J. L. B.; Pizani, P. S.; Gusmão, G. O. M.; Coutinho, H. D. M.; Oliveira, M. T. A.

2017-10-01

A new derivative of Meldrum's acid 5-((5-chloropyridin-2-ylamino)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (CYMM) of molecular formula C12H11ClN2O4 was synthesized and structurally characterized using single crystal X-ray diffraction technique. The vibrational properties of the crystal were studied by Fourier Transform infrared (FT-IR), Fourier Transform Raman (FT-Raman) techniques and theoretical calculations of quantum chemistry using Density functional theory (DFT) and Density functional perturbation theory (DFPT). A comparison with experimental spectra allowed the assignment of all the normal modes. The descriptions of the normal modes were carried by means of potential energy distribution (PED). Additionally, analysis of the antimicrobial activity and antibiotic resistance modulatory activity was carried out to evaluate the antibacterial potential of the CYMM.

Cardiac Complications, Earlier Treatment, and Initial Disease Severity in Kawasaki Disease.

PubMed

Abrams, Joseph Y; Belay, Ermias D; Uehara, Ritei; Maddox, Ryan A; Schonberger, Lawrence B; Nakamura, Yosikazu

2017-09-01

To assess if observed higher observed risks of cardiac complications for patients with Kawasaki disease (KD) treated earlier may reflect bias due to confounding from initial disease severity, as opposed to any negative effect of earlier treatment. We used data from Japanese nationwide KD surveys from 1997 to 2004. Receipt of additional intravenous immunoglobulin (IVIG) (data available all years) or any additional treatment (available for 2003-2004) were assessed as proxies for initial disease severity. We determined associations between earlier or later IVIG treatment (defined as receipt of IVIG on days 1-4 vs days 5-10 of illness) and cardiac complications by stratifying by receipt of additional treatment or by using logistic modeling to control for the effect of receiving additional treatment. A total of 48 310 patients with KD were included in the analysis. In unadjusted analysis, earlier IVIG treatment was associated with a higher risk for 4 categories of cardiac complications, including all major cardiac complications (risk ratio, 1.10; 95% CI, 1.06-1.15). Stratifying by receipt of additional treatment removed this association, and earlier IVIG treatment became protective against all major cardiac complications when controlling for any additional treatment in logistic regressions (OR, 0.90; 95% CI, 0.80-1.00). Observed higher risks of cardiac complications among patients with KD receiving IVIG treatment on days 1-4 of the illness are most likely due to underlying higher initial disease severity, and patients with KD should continue to be treated with IVIG as early as possible. Published by Elsevier Inc.

Travelling for earlier surgical treatment: the patient's view.

PubMed Central

Stewart, M; Donaldson, L J

1991-01-01

As part of the northern region's programme within the national waiting list initiative, schemes have been funded to test the feasibility and acceptability of offering patients the opportunity to travel further afield in order to receive earlier treatment. A total of 484 patients experiencing a long wait for routine surgical operations in the northern region were offered the opportunity to receive earlier treatment outside their local health district; 74% of the patients accepted the offer. The initiative was well received by the participating patients and the majority stated that if the need arose on a future occasion they would prefer to travel for treatment rather than have to wait for lengthy periods for treatment at their local hospital. These findings, interpreted in the light of the National Health Service reforms introduced in April 1991, suggest that for some types of care, patients would welcome greater flexibility in the placing of contracts, not merely reinforcement of historical patterns of referral. PMID:1823553

Calculation of evapotranspiration: Recursive and explicit methods

USDA-ARS?s Scientific Manuscript database

Crop yield is proportional to crop evapotranspiration (ETc) and it is important to calculate ETc correctly. Methods to calculate ETc have combined empirical and theoretical approaches. The combination method was used to calculate potential ETp. It is a combination method because it combined the ener...

Prescription stimulant use is associated with earlier onset of psychosis.

PubMed

Moran, Lauren V; Masters, Grace A; Pingali, Samira; Cohen, Bruce M; Liebson, Elizabeth; Rajarethinam, R P; Ongur, Dost

2015-12-01

A childhood history of attention deficit hyperactivity disorder (ADHD) is common in psychotic disorders, yet prescription stimulants may interact adversely with the physiology of these disorders. Specifically, exposure to stimulants leads to long-term increases in dopamine release. We therefore hypothesized that individuals with psychotic disorders previously exposed to prescription stimulants will have an earlier onset of psychosis. Age of onset of psychosis (AOP) was compared in individuals with and without prior exposure to prescription stimulants while controlling for potential confounding factors. In a sample of 205 patients recruited from an inpatient psychiatric unit, 40% (n = 82) reported use of stimulants prior to the onset of psychosis. Most participants were prescribed stimulants during childhood or adolescence for a diagnosis of ADHD. AOP was significantly earlier in those exposed to stimulants (20.5 vs. 24.6 years stimulants vs. no stimulants, p < 0.001). After controlling for gender, IQ, educational attainment, lifetime history of a cannabis use disorder or other drugs of abuse, and family history of a first-degree relative with psychosis, the association between stimulant exposure and earlier AOP remained significant. There was a significant gender × stimulant interaction with a greater reduction in AOP for females, whereas the smaller effect of stimulant use on AOP in males did not reach statistical significance. In conclusion, individuals with psychotic disorders exposed to prescription stimulants had an earlier onset of psychosis, and this relationship did not appear to be mediated by IQ or cannabis. Copyright © 2015 Elsevier Ltd. All rights reserved.

Theoretical calculating the thermodynamic properties of solid sorbents for CO{sub 2} capture applications

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

Duan, Yuhua

2012-11-02

Since current technologies for capturing CO{sub 2} to fight global climate change are still too energy intensive, there is a critical need for development of new materials that can capture CO{sub 2} reversibly with acceptable energy costs. Accordingly, solid sorbents have been proposed to be used for CO{sub 2} capture applications through a reversible chemical transformation. By combining thermodynamic database mining with first principles density functional theory and phonon lattice dynamics calculations, a theoretical screening methodology to identify the most promising CO{sub 2} sorbent candidates from the vast array of possible solid materials has been proposed and validated. The calculatedmore » thermodynamic properties of different classes of solid materials versus temperature and pressure changes were further used to evaluate the equilibrium properties for the CO{sub 2} adsorption/desorption cycles. According to the requirements imposed by the pre- and post- combustion technologies and based on our calculated thermodynamic properties for the CO{sub 2} capture reactions by the solids of interest, we were able to screen only those solid materials for which lower capture energy costs are expected at the desired pressure and temperature conditions. Only those selected CO{sub 2} sorbent candidates were further considered for experimental validations. The ab initio thermodynamic technique has the advantage of identifying thermodynamic properties of CO{sub 2} capture reactions without any experimental input beyond crystallographic structural information of the solid phases involved. Such methodology not only can be used to search for good candidates from existing database of solid materials, but also can provide some guidelines for synthesis new materials. In this presentation, we first introduce our screening methodology and the results on a testing set of solids with known thermodynamic properties to validate our methodology. Then, by applying our computational

Actinometric measurements and theoretical calculations of j/O3/, the rate of photolysis of ozone to O/1D/

NASA Technical Reports Server (NTRS)

Dickerson, R. R.; Stedman, D. H.; Chameides, W. L.; Crutzen, P. J.; Fishman, J.

1979-01-01

The paper presents an experimental technique which measures j/O3-O(1-D)/, the rate of solar photolysis of ozone to singlet oxygen atoms. It is shown that a flow actinometer carries dilute O3 in N2O into direct sunlight where the O(1D) formed reacts with N2O to form NO which chemiluminescence detects, with a time resolution of about one minute. Measurements indicate a photolysis rate of 1.2 (+ or - .2) x 10 to the -5/s for a cloudless sky, 45 deg zenith angle, 0.345 cm ozone column and zero albedo. Finally, ground level results compare with theoretical calculations based on the UV actinic flux as a function of ozone column and solar zenith angle.

Theoretical Calculations on the Feasibility of Microalgal Biofuels: Utilization of Marine Resources Could Help Realizing the Potential of Microalgae

PubMed Central

Park, Hanwool

2016-01-01

Abstract Microalgae have long been considered as one of most promising feedstocks with better characteristics for biofuels production over conventional energy crops. There have been a wide range of estimations on the feasibility of microalgal biofuels based on various productivity assumptions and data from different scales. The theoretical maximum algal biofuel productivity, however, can be calculated by the amount of solar irradiance and photosynthetic efficiency (PE), assuming other conditions are within the optimal range. Using the actual surface solar irradiance data around the world and PE of algal culture systems, maximum algal biomass and biofuel productivities were calculated, and feasibility of algal biofuel were assessed with the estimation. The results revealed that biofuel production would not easily meet the economic break‐even point and may not be sustainable at a large‐scale with the current algal biotechnology. Substantial reductions in the production cost, improvements in lipid productivity, recycling of resources, and utilization of non‐conventional resources will be necessary for feasible mass production of algal biofuel. Among the emerging technologies, cultivation of microalgae in the ocean shows great potentials to meet the resource requirements and economic feasibility in algal biofuel production by utilizing various marine resources. PMID:27782372

An Atomistic-Scale Study for Thermal Conductivity and Thermochemical Compatibility in (DyY)Zr2O7 Combining an Experimental Approach with Theoretical Calculation.

PubMed

Qu, Liu; Choy, Kwang-Leong; Wheatley, Richard

2016-02-18

Ceramic oxides that have high-temperature capabilities can be deposited on the superalloy components in aero engines and diesel engines to advance engine efficiency and reduce fuel consumption. This paper aims to study doping effects of Dy(3+) and Y(3+)on the thermodynamic properties of ZrO2 synthesized via a sol-gel route for a better control of the stoichiometry, combined with molecular dynamics (MD) simulation for the calculation of theoretical properties. The thermal conductivity is investigated by the MD simulation and Clarke's model. This can improve the understanding of the microstructure and thermodynamic properties of (DyY)Zr2O7 (DYZ) at the atomistic level. The phonon-defect scattering and phonon-phonon scattering processes are investigated via the theoretical calculation, which provides an effective way to study thermal transport properties of ionic oxides. The measured and predicted thermal conductivity of DYZ is lower than that of 4 mol % Y2O3 stabilized ZrO2 (4YSZ). It is discovered that DYZ is thermochemically compatible with Al2O3 at 1300 °C, whereas at 1350 °C DYZ reacts with Al2O3 forming a small amount of new phases.

An Atomistic-Scale Study for Thermal Conductivity and Thermochemical Compatibility in (DyY)Zr2O7 Combining an Experimental Approach with Theoretical Calculation

PubMed Central

Qu, Liu; Choy, Kwang-Leong; Wheatley, Richard

2016-01-01

Ceramic oxides that have high-temperature capabilities can be deposited on the superalloy components in aero engines and diesel engines to advance engine efficiency and reduce fuel consumption. This paper aims to study doping effects of Dy3+ and Y3+on the thermodynamic properties of ZrO2 synthesized via a sol-gel route for a better control of the stoichiometry, combined with molecular dynamics (MD) simulation for the calculation of theoretical properties. The thermal conductivity is investigated by the MD simulation and Clarke’s model. This can improve the understanding of the microstructure and thermodynamic properties of (DyY)Zr2O7 (DYZ) at the atomistic level. The phonon-defect scattering and phonon-phonon scattering processes are investigated via the theoretical calculation, which provides an effective way to study thermal transport properties of ionic oxides. The measured and predicted thermal conductivity of DYZ is lower than that of 4 mol % Y2O3 stabilized ZrO2 (4YSZ). It is discovered that DYZ is thermochemically compatible with Al2O3 at 1300 °C, whereas at 1350 °C DYZ reacts with Al2O3 forming a small amount of new phases. PMID:26888438

Probing Chemical Bonding and Electronic Structures in ThO- by Anion Photoelectron Imaging and Theoretical Calculations.

PubMed

Li, Yanli; Zou, Jinghan; Xiong, Xiao-Gen; Su, Jing; Xie, Hua; Fei, Zejie; Tang, Zichao; Liu, Hongtao

2017-03-16

Because of renewed research on thorium-based molten salt reactors, there is growing demand and interest in enhancing the knowledge of thorium chemistry both experimentally and theoretically. Compared with uranium, thorium has few chemical studies reported up to the present. Here we report the vibrationally resolved photoelectron imaging of the thorium monoxide anion. The electron affinity of ThO is first reported to be 0.707 ± 0.020 eV. Vibrational frequencies of the ThO molecule and its anion are determined from Franck-Condon simulation. Spectroscopic evidence is obtained for the two-electron transition in ThO - , indicating the strong electron correlation among the (7s σ ) 2 (6d δ ) 1 electrons in ThO - and the (7s σ ) 2 electrons in ThO. These findings are explained by using quantum-chemical calculations including spin-orbit coupling, and the chemical bonding of gaseous ThO molecules is analyzed. The present work will enrich our understanding of bonding capacities with the 6d valence shell.

Theoretical Grounds for the Propagation of Uncertainties in Monte Carlo Particle Transport

NASA Astrophysics Data System (ADS)

Saracco, Paolo; Pia, Maria Grazia; Batic, Matej

2014-04-01

We introduce a theoretical framework for the calculation of uncertainties affecting observables produced by Monte Carlo particle transport, which derive from uncertainties in physical parameters input into simulation. The theoretical developments are complemented by a heuristic application, which illustrates the method of calculation in a streamlined simulation environment.

Theoretical Calculation and Validation of the Water Vapor Continuum Absorption

NASA Technical Reports Server (NTRS)

Ma, Qiancheng; Tipping, Richard H.

1998-01-01

The primary objective of this investigation is the development of an improved parameterization of the water vapor continuum absorption through the refinement and validation of our existing theoretical formalism. The chief advantage of our approach is the self-consistent, first principles, basis of the formalism which allows us to predict the frequency, temperature and pressure dependence of the continuum absorption as well as provide insights into the physical mechanisms responsible for the continuum absorption. Moreover, our approach is such that the calculated continuum absorption can be easily incorporated into satellite retrieval algorithms and climate models. Accurate determination of the water vapor continuum is essential for the next generation of retrieval algorithms which propose to use the combined constraints of multispectral measurements such as those under development for EOS data analysis (e.g., retrieval algorithms based on MODIS and AIRS measurements); current Pathfinder activities which seek to use the combined constraints of infrared and microwave (e.g., HIRS and MSU) measurements to improve temperature and water profile retrievals, and field campaigns which seek to reconcile spectrally-resolved and broad-band measurements such as those obtained as part of FIRE. Current widely used continuum treatments have been shown to produce spectrally dependent errors, with the magnitude of the error dependent on temperature and abundance which produces errors with a seasonal and latitude dependence. Translated into flux, current water vapor continuum parameterizations produce flux errors of order 10 W/sq m, which compared to the 4 W/sq m magnitude of the greenhouse gas forcing and the 1-2 W/sq m estimated aerosol forcing is certainly climatologically significant and unacceptably large. While it is possible to tune the empirical formalisms, the paucity of laboratory measurements, especially at temperatures of interest for atmospheric applications, preclude

Theoretical Calculation and Validation of the Water Vapor Continuum Absorption

NASA Technical Reports Server (NTRS)

Ma, Qiancheng; Tipping, Richard H.

1998-01-01

The primary objective of this investigation is the development of an improved parameterization of the water vapor continuum absorption through the refinement and validation of our existing theoretical formalism. The chief advantage of our approach is the self-consistent, first principles, basis of the formalism which allows us to predict the frequency, temperature and pressure dependence of the continuum absorption as well as provide insights into the physical mechanisms responsible for the continuum absorption. Moreover, our approach is such that the calculated continuum absorption can be easily incorporated into satellite retrieval algorithms and climate models. Accurate determination of the water vapor continuum is essential for the next generation of retrieval algorithms which propose to use the combined constraints of multi-spectral measurements such as those under development for EOS data analysis (e.g., retrieval algorithms based on MODIS and AIRS measurements); current Pathfinder activities which seek to use the combined constraints of infrared and microwave (e.g., HIRS and MSU) measurements to improve temperature and water profile retrievals, and field campaigns which seek to reconcile spectrally-resolved and broad-band measurements such as those obtained as part of FIRE. Current widely used continuum treatments have been shown to produce spectrally dependent errors, with the magnitude of the error dependent on temperature and abundance which produces errors with a seasonal and latitude dependence. Translated into flux, current water vapor continuum parameterizations produce flux errors of order 10 W/ml, which compared to the 4 W/m' magnitude of the greenhouse gas forcing and the 1-2 W/m' estimated aerosol forcing is certainly climatologically significant and unacceptably large. While it is possible to tune the empirical formalisms, the paucity of laboratory measurements, especially at temperatures of interest for atmospheric applications, preclude tuning

Feeding biomechanics and theoretical calculations of bite force in bull sharks (Carcharhinus leucas) during ontogeny.

PubMed

Habegger, Maria L; Motta, Philip J; Huber, Daniel R; Dean, Mason N

2012-12-01

Evaluations of bite force, either measured directly or calculated theoretically, have been used to investigate the maximum feeding performance of a wide variety of vertebrates. However, bite force studies of fishes have focused primarily on small species due to the intractable nature of large apex predators. More massive muscles can generate higher forces and many of these fishes attain immense sizes; it is unclear how much of their biting performance is driven purely by dramatic ontogenetic increases in body size versus size-specific selection for enhanced feeding performance. In this study, we investigated biting performance and feeding biomechanics of immature and mature individuals from an ontogenetic series of an apex predator, the bull shark, Carcharhinus leucas (73-285cm total length). Theoretical bite force ranged from 36 to 2128N at the most anterior bite point, and 170 to 5914N at the most posterior bite point over the ontogenetic series. Scaling patterns differed among the two age groups investigated; immature bull shark bite force scaled with positive allometry, whereas adult bite force scaled isometrically. When the bite force of C. leucas was compared to those of 12 other cartilaginous fishes, bull sharks presented the highest mass-specific bite force, greater than that of the white shark or the great hammerhead shark. A phylogenetic independent contrast analysis of anatomical and dietary variables as determinants of bite force in these 13 species indicated that the evolution of large adult bite forces in cartilaginous fishes is linked predominantly to the evolution of large body size. Multiple regressions based on mass-specific standardized contrasts suggest that the evolution of high bite forces in Chondrichthyes is further correlated with hypertrophication of the jaw adductors, increased leverage for anterior biting, and widening of the head. Lastly, we discuss the ecological significance of positive allometry in bite force as a possible

Biological consequences of earlier snowmelt from desert dust deposition in alpine landscapes.

PubMed

Steltzer, Heidi; Landry, Chris; Painter, Thomas H; Anderson, Justin; Ayres, Edward

2009-07-14

Dust deposition to mountain snow cover, which has increased since the late 19(th) century, accelerates the rate of snowmelt by increasing the solar radiation absorbed by the snowpack. Snowmelt occurs earlier, but is decoupled from seasonal warming. Climate warming advances the timing of snowmelt and early season phenological events (e.g., the onset of greening and flowering); however, earlier snowmelt without warmer temperatures may have a different effect on phenology. Here, we report the results of a set of snowmelt manipulations in which radiation-absorbing fabric and the addition and removal of dust from the surface of the snowpack advanced or delayed snowmelt in the alpine tundra. These changes in the timing of snowmelt were superimposed on a system where the timing of snowmelt varies with topography and has been affected by increased dust loading. At the community level, phenology exhibited a threshold response to the timing of snowmelt. Greening and flowering were delayed before seasonal warming, after which there was a linear relationship between the date of snowmelt and the timing of phenological events. Consequently, the effects of earlier snowmelt on phenology differed in relation to topography, which resulted in increasing synchronicity in phenology across the alpine landscape with increasingly earlier snowmelt. The consequences of earlier snowmelt from increased dust deposition differ from climate warming and include delayed phenology, leading to synchronized growth and flowering across the landscape and the opportunity for altered species interactions, landscape-scale gene flow via pollination, and nutrient cycling.

Automated Routines for Calculating Whole-Stream Metabolism: Theoretical Background and User's Guide

USGS Publications Warehouse

Bales, Jerad D.; Nardi, Mark R.

2007-01-01

In order to standardize methods and facilitate rapid calculation and archival of stream-metabolism variables, the Stream Metabolism Program was developed to calculate gross primary production, net ecosystem production, respiration, and selected other variables from continuous measurements of dissolved-oxygen concentration, water temperature, and other user-supplied information. Methods for calculating metabolism from continuous measurements of dissolved-oxygen concentration and water temperature are fairly well known, but a standard set of procedures and computation software for all aspects of the calculations were not available previously. The Stream Metabolism Program addresses this deficiency with a stand-alone executable computer program written in Visual Basic.NET?, which runs in the Microsoft Windows? environment. All equations and assumptions used in the development of the software are documented in this report. Detailed guidance on application of the software is presented, along with a summary of the data required to use the software. Data from either a single station or paired (upstream, downstream) stations can be used with the software to calculate metabolism variables.

Tektite ablation - Some confirming calculations.

NASA Technical Reports Server (NTRS)

O'Keefe, J. A., III; Silver, A. D.; Cameron, W. S.; Adams , E. W.; Warmbrod, J. D.

1973-01-01

The calculation of tektite ablation has been redone, taking into account transient effects, internal radiation, melting and nonequilibrium vaporization of the glass, and the drag effect of the flanges. It is found that the results confirm the earlier calculations of Chapman and his group and of Adams and his co-workers. The general trend of the results is not sensitive to reasonable changes of the physical parameters. The ablation is predominantly by melting rather than by vaporization at all velocities up to 11 km/sec; this is surprising in view of the lack of detectable melt flow in most tektites. Chemical effects have not been considered.

Theoretical study of thorium monoxide for the electron electric dipole moment search: electronic properties of H(3)Δ(1) in ThO.

PubMed

Skripnikov, L V; Titov, A V

2015-01-14

Recently, improved limits on the electron electric dipole moment, and dimensionless constant, kT,P, characterizing the strength of the T,P-odd pseudoscalar-scalar electron-nucleus neutral current interaction in the H(3)Δ1 state of ThO molecule were obtained by the ACME collaboration [J. Baron et al., Science 343, 269 (2014)]. The interpretation of the experiment in terms of these fundamental quantities is based on the results of theoretical study of appropriate ThO characteristics, the effective electric field acting on electron, Eeff, and a parameter of the T,P-odd pseudoscalar-scalar interaction, WT,P, given in Skripnikov et al. [J. Chem. Phys. 139, 221103 (2013)] by St. Petersburg group. To reduce the uncertainties of the given limits, we report improved calculations of the molecular state-specific quantities Eeff, 81.5 GV/cm, and WT,P, 112 kHz, with the uncertainty within 7% of the magnitudes. Thus, the values recommended to use for the upper limits of the quantities are 75.8 GV/cm and 104 kHz, correspondingly. The hyperfine structure constant, molecule-frame dipole moment of the H(3)Δ1 state, and the H(3)Δ1 → X(1)Σ(+) transition energy which, in general, can serve as a measure of reliability of the obtained Eeff and WT,P values are also calculated. In addition, we report the first calculation of g-factor for the H(3)Δ1 state of ThO. The results are compared to the earlier experimental and theoretical studies, and a detailed analysis of uncertainties of the calculations is given.

Theoretical Calculations on Sediment Transport on Titan, and the Possible Production of Streamlined Forms

NASA Technical Reports Server (NTRS)

Burr, D. M.; Emery, J. P.; Lorenz, R. D.

2005-01-01

The Cassini Imaging Science System (ISS) has been returning images of Titan, along with other Saturnian satellites. Images taken through the 938 nm methane window see down to Titan's surface. One of the purposes of the Cassini mission is to investigate possible fluid cycling on Titan. Lemniscate features shown recently and radar evidence of surface flow prompted us to consider theoretically the creation by methane fluid flow of streamlined forms on Titan. This follows work by other groups in theoretical consideration of fluid motion on Titan's surface.

Calculation of Temperature Rise in Calorimetry.

ERIC Educational Resources Information Center

Canagaratna, Sebastian G.; Witt, Jerry

1988-01-01

Gives a simple but fuller account of the basis for accurately calculating temperature rise in calorimetry. Points out some misconceptions regarding these calculations. Describes two basic methods, the extrapolation to zero time and the equal area method. Discusses the theoretical basis of each and their underlying assumptions. (CW)

Calculation of three-dimensional compressible laminar and turbulent boundary layers. Calculation of three-dimensional compressible boundary layers on arbitrary wings

NASA Technical Reports Server (NTRS)

Cebeci, T.; Kaups, K.; Ramsey, J.; Moser, A.

1975-01-01

A very general method for calculating compressible three-dimensional laminar and turbulent boundary layers on arbitrary wings is described. The method utilizes a nonorthogonal coordinate system for the boundary-layer calculations and includes a geometry package that represents the wing analytically. In the calculations all the geometric parameters of the coordinate system are accounted for. The Reynolds shear-stress terms are modeled by an eddy-viscosity formulation developed by Cebeci. The governing equations are solved by a very efficient two-point finite-difference method used earlier by Keller and Cebeci for two-dimensional flows and later by Cebeci for three-dimensional flows.

Torsional energy levels of CH₃OH⁺/CH₃OD⁺/CD₃OD⁺ studied by zero-kinetic energy photoelectron spectroscopy and theoretical calculations.

PubMed

Dai, Zuyang; Gao, Shuming; Wang, Jia; Mo, Yuxiang

2014-10-14

The torsional energy levels of CH3OH(+), CH3OD(+), and CD3OD(+) have been determined for the first time using one-photon zero kinetic energy photoelectron spectroscopy. The adiabatic ionization energies for CH3OH, CH3OD, and CD3OD are determined as 10.8396, 10.8455, and 10.8732 eV with uncertainties of 0.0005 eV, respectively. Theoretical calculations have also been performed to obtain the torsional energy levels for the three isotopologues using a one-dimensional model with approximate zero-point energy corrections of the torsional potential energy curves. The calculated values are in good agreement with the experimental data. The barrier height of the torsional potential energy without zero-point energy correction was calculated as 157 cm(-1), which is about half of that of the neutral (340 cm(-1)). The calculations showed that the cation has eclipsed conformation at the energy minimum and staggered one at the saddle point, which is the opposite of what is observed in the neutral molecule. The fundamental C-O stretch vibrational energy level for CD3OD(+) has also been determined. The energy levels for the combinational excitation of the torsional vibration and the fundamental C-O stretch vibration indicate a strong torsion-vibration coupling.

Theoretical Calculations on the Feasibility of Microalgal Biofuels: Utilization of Marine Resources Could Help Realizing the Potential of Microalgae.

PubMed

Park, Hanwool; Lee, Choul-Gyun

2016-11-01

Microalgae have long been considered as one of most promising feedstocks with better characteristics for biofuels production over conventional energy crops. There have been a wide range of estimations on the feasibility of microalgal biofuels based on various productivity assumptions and data from different scales. The theoretical maximum algal biofuel productivity, however, can be calculated by the amount of solar irradiance and photosynthetic efficiency (PE), assuming other conditions are within the optimal range. Using the actual surface solar irradiance data around the world and PE of algal culture systems, maximum algal biomass and biofuel productivities were calculated, and feasibility of algal biofuel were assessed with the estimation. The results revealed that biofuel production would not easily meet the economic break-even point and may not be sustainable at a large-scale with the current algal biotechnology. Substantial reductions in the production cost, improvements in lipid productivity, recycling of resources, and utilization of non-conventional resources will be necessary for feasible mass production of algal biofuel. Among the emerging technologies, cultivation of microalgae in the ocean shows great potentials to meet the resource requirements and economic feasibility in algal biofuel production by utilizing various marine resources. © 2016 The Authors. Biotechnology Journal published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Nonlocal Calculation of Circumstellar OH Masers

NASA Astrophysics Data System (ADS)

Collison, A. J.; Nedoluha, G. E.

1993-12-01

We present calculations for circumstellar OH masers which explicitly account for the nonlocal interaction throughout the masing region. Excitation temperatures and observed emission are calculated for all four ground state maser lines. All other transitions are treated using a modified Sobolev approximation. Calculations are performed within the context of a simplified dust/outflow model which provides the pumping conditions and their variation with radius. Total velocity relaxation is implicitly assumed in the calculations. We find general agreement with the qualitative results of earlier work (Collison & Nedoluha, ApJ, 10 Feb 94 issue) and agree with the conclusions of Alcock & Ross (1986, ApJ, 305, 837) who showed that observed profiles can not be produced by a smooth, spherically symmetric wind model of the outflow.

Vibrational spectroscopic study, structural analysis, photophysical properties and theoretical calculations of cis-(±)-2,4,5-tris(pyridin-2-yl)imidazoline

NASA Astrophysics Data System (ADS)

Baldenebro-López, Jesús; Báez-Castro, Alberto; Glossman-Mitnik, Daniel; Höpfl, Herbert; Cruz-Enríquez, Adriana; Miranda-Soto, Valentín; Parra-Hake, Miguel; Campos-Gaxiola, José J.

2017-02-01

cis-(±)-2,4,5-tris(pyridin-2-yl)imidazoline has been fully characterized by FT-IR, FT-Raman, UV-Vis and fluorescence spectroscopy, one- and two-dimensional NMR spectroscopy (1H, 1H-1H gCOSY, 1H-1H gNOESY,13C{1H} ATP, 1H-13C and 1H-15N gHSQC and 1H-13C gHMBC), high-resolution mass spectrometry (HR-FAB+), TG-DSC analysis and low-temperature single-crystal X-ray diffraction analysis. Additionally, the molecular geometry and the vibrational infrared and Raman frequencies were calculated by density functional theory using the M06/6-31G(d) level of theory, showing good agreement with the experimental results. The title compound showed interesting photophysical properties, which were studied experimentally in solution and in the solid state by UV-Vis and fluorescence spectroscopy and compared to the theoretically obtained parameters using TD-DFT calculations. Natural and Mulliken atomic charges and the molecular electrostatic potential (MEP) have been mapped.

Numerical calculation of the Fresnel transform.

PubMed

Kelly, Damien P

2014-04-01

In this paper, we address the problem of calculating Fresnel diffraction integrals using a finite number of uniformly spaced samples. General and simple sampling rules of thumb are derived that allow the user to calculate the distribution for any propagation distance. It is shown how these rules can be extended to fast-Fourier-transform-based algorithms to increase calculation efficiency. A comparison with other theoretical approaches is made.

Validation of NASCAP-2K Spacecraft-Environment Interactions Calculations

NASA Technical Reports Server (NTRS)

Davis, V. A.; Mandell, M. J.; Gardner, B. M.; Mikellides, I. G.; Neergaard, L. F.; Cooke, D. L.; Minor, J.

2004-01-01

The recently released Nascap-2k, version 2.0, three-dimensional computer code models interactions between spacecraft surfaces and low-earth-orbit, geosynchronous, auroral, and interplanetary plasma environments. It replaces the earlier three-dimensional spacecraft interactions codes NASCAP/GEO, NASCAP/LEO, POLAR, and DynaPAC. Nascap-2k has improved numeric techniques, a modern user interface, and a simple, interactive satellite surface definition module (Object ToolKit). We establish the accuracy of Nascap-2k both by comparing computed currents and potentials with analytic results and by comparing Nascap-2k results with published calculations using the earlier codes. Nascap-2k predicts Langmuir-Blodgett or Parker-Murphy current collection for a nearly spherical (100 surfaces) satellite in a short Debye length plasma depending on the absence or presence of a magnetic field. A low fidelity (in geometry and time) Nascap-2k geosynchronous charging calculation gives the same results as the corresponding low fidelity NASCAP/GEO calculation. A high fidelity calculation (using the Nascap-2k improved geometry and time stepping capabilities) gives higher potentials, which are more consistent with typical observations. Nascap-2k predicts the same current as a function of applied potential as was observed and calculated by NASCAP/LEO for the SPEAR I rocket with a bipolar sheath. A Nascap-2k DMSP charging calculation gives results similar to those obtained using POLAR and consistent with observation.

Comment on linewidths and shifts in the Stokes-Raman Q branch of D2 in He

NASA Technical Reports Server (NTRS)

Green, Sheldon; Blackmore, Robert; Monchick, Louis

1989-01-01

Collision-induced widths and shifts for Raman Q-branch transitions of D2 in He were calculated from S matrices obtained with converged close coupling scattering calculations on an accurate theoretical interaction potential. Results agree well with experimental values. Discrepancies between experimental line shifts and theoretical values from an earlier study (Blackmore et al., 1988) are traced to a computational error in that work. The effects of vibrational inelasticity and of centrifugal distortion on energy levels and on potential matrix elements, all of which were ignored in the earlier study, are explicitly considered here and found to be small.

Theoretical studies of dissociative recombination

NASA Technical Reports Server (NTRS)

Guberman, S. L.

1985-01-01

The calculation of dissociative recombination rates and cross sections over a wide temperature range by theoretical quantum chemical techniques is described. Model calculations on electron capture by diatomic ions are reported which illustrate the dependence of the rates and cross sections on electron energy, electron temperature, and vibrational temperature for three model crossings of neutral and ionic potential curves. It is shown that cross sections for recombination to the lowest vibrational level of the ion can vary by several orders of magnitude depending upon the position of the neutral and ionic potential curve crossing within the turning points of the v = 1 vibrational level. A new approach for calculating electron capture widths is reported. Ab initio calculations are described for recombination of O2(+) leading to excited O atoms.

A new theoretical approach to adsorption desorption behavior of Ga on GaAs surfaces

NASA Astrophysics Data System (ADS)

Kangawa, Y.; Ito, T.; Taguchi, A.; Shiraishi, K.; Ohachi, T.

2001-11-01

We propose a new theoretical approach for studying adsorption-desorption behavior of atoms on semiconductor surfaces. The new theoretical approach based on the ab initio calculations incorporates the free energy of gas phase; therefore we can calculate how adsorption and desorption depends on growth temperature and beam equivalent pressure (BEP). The versatility of the new theoretical approach was confirmed by the calculation of Ga adsorption-desorption transition temperatures and transition BEPs on the GaAs(0 0 1)-(4×2)β2 Ga-rich surface. This new approach is feasible to predict how adsorption and desorption depend on the growth conditions.

Theoretical Investigation of Calculating Temperatures in the Combining Zone of Cu/Fe Composite Plate Jointed by Explosive Welding

NASA Astrophysics Data System (ADS)

Qu, Y. D.; Zhang, W. J.; Kong, X. Q.; Zhao, X.

2016-03-01

The heat-transfer behavior of the interface of Flyer plate (or Base Plate) has great influence on the microcosmic structures, stress distributions, and interface distortion of the welded interface of composite plates by explosive welding. In this paper, the temperature distributions in the combing zone are studied for the case of Cu/Fe composite plate jointed by explosive welding near the lower limit of explosive welding. The results show that Flyer plate (Cu plate) and Base Plate (Fe plate) firstly almost have the same melting rate in the explosive welding process. Then, the melting rate of Cu plate becomes higher than that of Fe plate. Finally, the melt thicknesses of Cu plate and Fe plate trend to be different constants, respectively. Meanwhile, the melting layer of Cu plate is thicker than that of Fe plate. The research could supply some theoretical foundations for calculating the temperature distribution and optimizing the explosive welding parameters of Cu/Fe composite plate to some extent.

Verification of Internal Dose Calculations.

NASA Astrophysics Data System (ADS)

Aissi, Abdelmadjid

The MIRD internal dose calculations have been in use for more than 15 years, but their accuracy has always been questionable. There have been attempts to verify these calculations; however, these attempts had various shortcomings which kept the question of verification of the MIRD data still unanswered. The purpose of this research was to develop techniques and methods to verify the MIRD calculations in a more systematic and scientific manner. The research consisted of improving a volumetric dosimeter, developing molding techniques, and adapting the Monte Carlo computer code ALGAM to the experimental conditions and vice versa. The organic dosimetric system contained TLD-100 powder and could be shaped to represent human organs. The dosimeter possessed excellent characteristics for the measurement of internal absorbed doses, even in the case of the lungs. The molding techniques are inexpensive and were used in the fabrication of dosimetric and radioactive source organs. The adaptation of the computer program provided useful theoretical data with which the experimental measurements were compared. The experimental data and the theoretical calculations were compared for 6 source organ-7 target organ configurations. The results of the comparison indicated the existence of an agreement between measured and calculated absorbed doses, when taking into consideration the average uncertainty (16%) of the measurements, and the average coefficient of variation (10%) of the Monte Carlo calculations. However, analysis of the data gave also an indication that the Monte Carlo method might overestimate the internal absorbed doses. Even if the overestimate exists, at least it could be said that the use of the MIRD method in internal dosimetry was shown to lead to no unnecessary exposure to radiation that could be caused by underestimating the absorbed dose. The experimental and the theoretical data were also used to test the validity of the Reciprocity Theorem for heterogeneous

Comparing Ultraviolet Spectra against Calculations: Year 2 Results

NASA Technical Reports Server (NTRS)

Peterson, Ruth C.

2004-01-01

The five-year goal of this effort is to calculate high fidelity mid-W spectra for individual stars and stellar systems for a wide range of ages, abundances, and abundance ratios. In this second year, the comparison of our calculations against observed high-resolution mid- W spectra was extended to stars as metal-rich as the Sun, and to hotter and cooler stars, further improving the list of atomic line parameters used in the calculations. We also published the application of our calculations based on the earlier list of line parameters to the observed mid-UV and optical spectra of a mildly metal-poor globular cluster in the nearby Andromeda galaxy, Messier 3 1.

Absorption coefficients of silicon: A theoretical treatment

NASA Astrophysics Data System (ADS)

Tsai, Chin-Yi

2018-05-01

A theoretical model with explicit formulas for calculating the optical absorption and gain coefficients of silicon is presented. It incorporates direct and indirect interband transitions and considers the effects of occupied/unoccupied carrier states. The indirect interband transition is calculated from the second-order time-independent perturbation theory of quantum mechanics by incorporating all eight possible routes of absorption or emission of photons and phonons. Absorption coefficients of silicon are calculated from these formulas. The agreements and discrepancies among the calculated results, the Rajkanan-Singh-Shewchun (RSS) formula, and Green's data are investigated and discussed. For example, the RSS formula tends to overestimate the contributions of indirect transitions for cases with high photon energy. The results show that the state occupied/unoccupied effect is almost negligible for silicon absorption coefficients up to the onset of the optical gain condition where the energy separation of Quasi-Femi levels between electrons and holes is larger than the band-gap energy. The usefulness of using the physics-based formulas, rather than semi-empirical fitting ones, for absorption coefficients in theoretical studies of photovoltaic devices is also discussed.

Pocket calculator for local fire-danger ratings

Treesearch

Richard J. Barney; William C. Fischer

1967-01-01

In 1964, Stockstad and Barney published tables that provided conversion factors for calculating local fire danger in the Intermountain area according to fuel types, locations, steepness of terrain, aspects, and times of day. These tables were based on the National Fire-Danger Rating System published earlier that year. This system was adopted for operational use in...

When VSEPR Fails: Experimental and Theoretical Investigations of the Behavior of Alkaline-Earth-Metal Acetylides

PubMed Central

Guino-o, Marites A.; Alexander, Jacob S.; McKee, Michael L.; Hope, Håkon; Englich, Ulrich B.

2014-01-01

The synthesis, structural, and spectral characterization as well as a theoretical study of a family of alkaline-earth-metal acetylides provides insights into synthetic access and the structural and bonding characteristics of this group of highly reactive compounds. Based on our earlier communication that reported unusual geometry for a family of triphenylsilyl-substituted alkaline-earth-metal acetylides, we herein present our studies on an expanded family of target derivatives, providing experimental and theoretical data to offer new insights into the intensively debated theme of structural chemistry in heavy alkaline-earth-metal chemistry. PMID:19844925

Does Speech Emerge from Earlier Appearing Oral Motor Behaviors?.

ERIC Educational Resources Information Center

Moore, Christopher A.; Ruark, Jacki L.

1996-01-01

This study of the oral motor behaviors of seven toddlers (age 15 months) may be interpreted to indicate that: (1) mandibular coordination follows a developmental continuum from earlier emerging behaviors, such as chewing and sucking, through babbling, to speech, or (2) unique task demands give rise to distinct mandibular coordinative constraints…

Three-dimensional Nonlinear Calculation of the 2017 North Korean Nuclear Test

NASA Astrophysics Data System (ADS)

Stevens, J. L.; O'Brien, M.

2017-12-01

We perform a three-dimensional nonlinear calculation of the 2017 North Korean Nuclear Test including the topography of the test site. Surface waves from all six DPRK nuclear tests are remarkably similar. Linear scaling of surface wave amplitudes from an estimated yield of 4.6 kt for the 2009 event (Murphy et al, 2013) gives an estimated yield of 180 kt for the 2017 event, which is the yield used in the calculation. The depth of the calculated explosion is 730 meters below the surface and close to the peak of Mt. Mantap. Calculated surface displacements are as large as 4 meters vertical and 2 meters horizontal, but there is a node in both with minimal vertical and horizontal displacements close to the mountain peak. Earlier calculations of a 12.5 kiloton explosion at depths of 100-800 meters show a peak in surface wave amplitudes for explosions at the base of the mountain relative to both deeper and shallower sources, so the North Korean explosions have been at optimal depth for surface wave generation. This combined with tectonic stress state and a low surface wave amplitude bias at other test sites may explain the large surface wave anomaly at this test site. Cracking and nonlinear deformation are much more extensive for the 180 kt calculation than in the earlier 12.5 kiloton calculations.

DOPPLER CALCULATIONS FOR LARGE FAST CERAMIC REACTORS--EFFECTS OF IMPROVED METHODS AND RECENT CROSS SECTION INFORMATION

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

Greebler, P.; Goldman, E.

1962-12-19

Doppler calculations for large fast ceramic reactors (FCR), using recent cross section information and improved methods, are described. Cross sections of U/sup 238/, Pu/sup 239/, and Pu/sup 210/ with fuel temperature variations needed for perturbation calculations of Doppler reactivity changes are tabulated as a function of potential scattering cross section per absorber isotope at energies below 400 kev. These may be used in Doppler calculations for anv fast reactor. Results of Doppler calculations on a large fast ceramic reactor are given to show the effects of the improved calculation methods and of recent cross secrion data on the calculated Dopplermore » coefficient. The updated methods and cross sections used yield a somewhat harder spectrum and accordingly a somewhat smaller Doppler coefficient for a given FCR core size and composition than calculated in earlier work, but they support the essential conclusion derived earlier that the Doppler effect provides an important safety advantage in a large FCR. 28 references. (auth)« less

Calculation of the critical temperature of a dilute Bose gas in the Bogoliubov approximation

NASA Astrophysics Data System (ADS)

Napiórkowski, M.; Reuvers, R.; Solovej, J. P.

2018-01-01

Following an earlier calculation in 3D, we calculate the 2D critical temperature of a dilute, translation-invariant Bose gas using a variational formulation of the Bogoliubov approximation introduced by Critchley and Solomon in 1976. This provides the first analytical calculation of the Kosterlitz-Thouless transition temperature that includes the constant in the logarithm.

Electron collisions with small esters: A joint experimental-theoretical investigation

NASA Astrophysics Data System (ADS)

de Souza, G. L. C.; da Silva, L. A.; de Sousa, W. J. C.; Sugohara, R. T.; Iga, I.; dos Santos, A. S.; Machado, L. E.; Homem, M. G. P.; Brescansin, L. M.; Lucchese, R. R.; Lee, M.-T.

2016-03-01

A theoretical and experimental investigation on elastic electron scattering by two small esters, namely, methyl formate and ethyl acetate, is reported. Experimental differential, integral, and momentum-transfer cross sections are given in the 30-1000 eV and 10∘-120∘ ranges. The relative-flow technique was used to determine such quantities. Particularly for methyl formate, a theoretical study was also carried out in the 1-500 eV range. A complex optical potential derived from a Hartree-Fock molecular wave function was used to represent the collision dynamics, whereas the Padé approximation was used to solve the scattering equations. In addition, calculations based on the framework of the independent-atom model (IAM) were also performed for both targets. In general, there is good agreement between our experimental data and the present theoretical results calculated using the Padé approximation. The theoretical results using the IAM also agree well with the experimental data at 200 eV and above. Moreover, for methyl formate, our calculations reveal a 2A'' (π*) resonance at about 3.0 eV and a σ*-type resonance centered at about 8.0 eV in the 2A' scattering channel. The π* resonance is also seen in other targets containing a carbonyl group.

Conformational energy calculations on polypeptides and proteins: use of a statistical mechanical procedure for evaluating structure and properties.

PubMed

Scheraga, H A; Paine, G H

1986-01-01

We are using a variety of theoretical and computational techniques to study protein structure, protein folding, and higher-order structures. Our earlier work involved treatments of liquid water and aqueous solutions of nonpolar and polar solutes, computations of the stabilities of the fundamental structures of proteins and their packing arrangements, conformations of small cyclic and open-chain peptides, structures of fibrous proteins (collagen), structures of homologous globular proteins, introduction of special procedures as constraints during energy minimization of globular proteins, and structures of enzyme-substrate complexes. Recently, we presented a new methodology for predicting polypeptide structure (described here); the method is based on the calculation of the probable and average conformation of a polypeptide chain by the application of equilibrium statistical mechanics in conjunction with an adaptive, importance sampling Monte Carlo algorithm. As a test, it was applied to Met-enkephalin.

Later endogenous circadian temperature nadir relative to an earlier wake time in older people

NASA Technical Reports Server (NTRS)

Duffy, J. F.; Dijk, D. J.; Klerman, E. B.; Czeisler, C. A.

1998-01-01

The contribution of the circadian timing system to the age-related advance of sleep-wake timing was investigated in two experiments. In a constant routine protocol, we found that the average wake time and endogenous circadian phase of 44 older subjects were earlier than that of 101 young men. However, the earlier circadian phase of the older subjects actually occurred later relative to their habitual wake time than it did in young men. These results indicate that an age-related advance of circadian phase cannot fully account for the high prevalence of early morning awakening in healthy older people. In a second study, 13 older subjects and 10 young men were scheduled to a 28-h day, such that they were scheduled to sleep at many circadian phases. Self-reported awakening from scheduled sleep episodes and cognitive throughput during the second half of the wake episode varied markedly as a function of circadian phase in both groups. The rising phase of both rhythms was advanced in the older subjects, suggesting an age-related change in the circadian regulation of sleep-wake propensity. We hypothesize that under entrained conditions, these age-related changes in the relationship between circadian phase and wake time are likely associated with self-selected light exposure at an earlier circadian phase. This earlier exposure to light could account for the earlier clock hour to which the endogenous circadian pacemaker is entrained in older people and thereby further increase their propensity to awaken at an even earlier time.

Theoretical foundations of the chronometric cosmology.

PubMed

Segal, I E

1976-03-01

The derivation of the redshift (z)-distance (r) relation in the chronometric theory of the Cosmos is amplified. The basic physical quantities are represented by precisely defined self-adjoint operators in global Hilbert spaces. Computations yielding explicit bounds for the deviation of the theoretical prediction from the relation z = tan(2)(r/2R) (where R denotes the radius of the universe), earlier derived employing less formal procedures, are carried out for: (a) a cut-off plane wave in two dimensions; (b) a scalar spherical wave in four dimensions; (c) the same as (b) with appropriate incorporation of the photon spin. Both this deviation and the (quantum) dispersion in redshift are shown to be unobservably small. A parallel classical treatment is possible and leads to similar results.

Calculation of binary magnetic properties and potential energy curve in xenon dimer: second virial coefficient of (129)Xe nuclear shielding.

PubMed

Hanni, Matti; Lantto, Perttu; Runeberg, Nino; Jokisaari, Jukka; Vaara, Juha

2004-09-22

Quantum chemical calculations of the nuclear shielding tensor, the nuclear quadrupole coupling tensor, and the spin-rotation tensor are reported for the Xe dimer using ab initio quantum chemical methods. The binary chemical shift delta, the anisotropy of the shielding tensor Delta sigma, the nuclear quadrupole coupling tensor component along the internuclear axis chi( parallel ), and the spin-rotation constant C( perpendicular ) are presented as a function of internuclear distance. The basis set superposition error is approximately corrected for by using the counterpoise correction (CP) method. Electron correlation effects are systematically studied via the Hartree-Fock, complete active space self-consistent field, second-order Møller-Plesset many-body perturbation, and coupled-cluster singles and doubles (CCSD) theories, the last one without and with noniterative triples, at the nonrelativistic all-electron level. We also report a high-quality theoretical interatomic potential for the Xe dimer, gained using the relativistic effective potential/core polarization potential scheme. These calculations used valence basis set of cc-pVQZ quality supplemented with a set of midbond functions. The second virial coefficient of Xe nuclear shielding, which is probably the experimentally best-characterized intermolecular interaction effect in nuclear magnetic resonance spectroscopy, is computed as a function of temperature, and compared to experiment and earlier theoretical results. The best results for the second virial coefficient, obtained using the CCSD(CP) binary chemical shift curve and either our best theoretical potential or the empirical potentials from the literature, are in good agreement with experiment. Zero-point vibrational corrections of delta, Delta sigma, chi (parallel), and C (perpendicular) in the nu=0, J=0 rovibrational ground state of the xenon dimer are also reported.

Finite area combustor theoretical rocket performance

NASA Technical Reports Server (NTRS)

Gordon, Sanford; Mcbride, Bonnie J.

1988-01-01

Previous to this report, the computer program of NASA SP-273 and NASA TM-86885 was capable of calculating theoretical rocket performance based only on the assumption of an infinite area combustion chamber (IAC). An option was added to this program which now also permits the calculation of rocket performance based on the assumption of a finite area combustion chamber (FAC). In the FAC model, the combustion process in the cylindrical chamber is assumed to be adiabatic, but nonisentropic. This results in a stagnation pressure drop from the injector face to the end of the chamber and a lower calculated performance for the FAC model than the IAC model.

Reading-Related Skills in Earlier- and Later-Schooled Children

ERIC Educational Resources Information Center

Cunningham, Anna J.; Carroll, Julia M.

2011-01-01

We investigate the effects of age-related factors and formal instruction on the development of reading-related skills in children aged 4 and 7 years. Age effects were determined by comparing two groups of children at the onset of formal schooling; one aged 7 (later-schooled) and one aged 4 (earlier-schooled). Schooling effects were measured by…

Perceptual sensitivity to spectral properties of earlier sounds during speech categorization.

PubMed

Stilp, Christian E; Assgari, Ashley A

2018-02-28

Speech perception is heavily influenced by surrounding sounds. When spectral properties differ between earlier (context) and later (target) sounds, this can produce spectral contrast effects (SCEs) that bias perception of later sounds. For example, when context sounds have more energy in low-F 1 frequency regions, listeners report more high-F 1 responses to a target vowel, and vice versa. SCEs have been reported using various approaches for a wide range of stimuli, but most often, large spectral peaks were added to the context to bias speech categorization. This obscures the lower limit of perceptual sensitivity to spectral properties of earlier sounds, i.e., when SCEs begin to bias speech categorization. Listeners categorized vowels (/ɪ/-/ɛ/, Experiment 1) or consonants (/d/-/g/, Experiment 2) following a context sentence with little spectral amplification (+1 to +4 dB) in frequency regions known to produce SCEs. In both experiments, +3 and +4 dB amplification in key frequency regions of the context produced SCEs, but lesser amplification was insufficient to bias performance. This establishes a lower limit of perceptual sensitivity where spectral differences across sounds can bias subsequent speech categorization. These results are consistent with proposed adaptation-based mechanisms that potentially underlie SCEs in auditory perception. Recent sounds can change what speech sounds we hear later. This can occur when the average frequency composition of earlier sounds differs from that of later sounds, biasing how they are perceived. These "spectral contrast effects" are widely observed when sounds' frequency compositions differ substantially. We reveal the lower limit of these effects, as +3 dB amplification of key frequency regions in earlier sounds was enough to bias categorization of the following vowel or consonant sound. Speech categorization being biased by very small spectral differences across sounds suggests that spectral contrast effects occur

Theoretical development and first-principles analysis of strongly correlated systems

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

Liu, Chen

A variety of quantum many-body methods have been developed for studying the strongly correlated electron systems. We have also proposed a computationally efficient and accurate approach, named the correlation matrix renormalization (CMR) method, to address the challenges. The initial implementation of the CMR method is designed for molecules which have theoretical advantages, including small size of system, manifest mechanism and strongly correlation effect such as bond breaking process. The theoretic development and benchmark tests of the CMR method are included in this thesis. Meanwhile, ground state total energy is the most important property of electronic calculations. We also investigated anmore » alternative approach to calculate the total energy, and extended this method for magnetic anisotropy energy (MAE) of ferromagnetic materials. In addition, another theoretical tool, dynamical mean- field theory (DMFT) on top of the DFT , has also been used in electronic structure calculations for an Iridium oxide to study the phase transition, which results from an interplay of the d electrons' internal degrees of freedom.« less

A systematic theoretical study of the electronic structures of porphyrin dimers: DFT and TD-DFT calculations on diporphyrins linked by ethane, ethene, ethyne, imine, and azo bridges.

PubMed

Rintoul, Llew; Harper, Shannon R; Arnold, Dennis P

2013-11-21

Theoretical calculations of the geometries, electronic structures and electronic absorption spectra of a series of covalently-linked porphyrin dimers are reported. The diporphyrins comprise 5,10,15-triphenylporphyrinatozinc(II) (ZnTriPP) units linked through the meso carbons by two-atom bridges, namely 1,2-ethanediyl (1), trans-1,2-ethenediyl (2), ethynediyl (3), 1,2-iminomethenediyl (4), and transdiazenediyl (5). The structures were optimised in toluene solvent by Density Functional Theory (DFT), using the integral equation formalism variant of the polarizable continuum model. The calculations were performed using the B3LYP functional and the 6-31G(d,p) basis set. The complete molecules were modelled, with no substitution of smaller groups on the periphery. In parallel, the compounds 2–5 were prepared by known or novel synthetic routes, to enable comparisons of experimental electronic absorption spectra with those calculated using time dependent-DFT at the same level of theory. As the ethane dimer 1 is not yet synthetically accessible, the model monomer meso-2-phenylethylZnTriPP was used for comparisons with the theoretical predictions. The results form a self-consistent set, enabling for the first time legitimate comparisons of the electronic structures of the series, especially regarding the degree to which the porphyrin p-systems interact by conjugation across the bridges. The theoretical calculations of the electronic transitions match the observed spectra in toluene to a remarkable degree, especially with respect to the peak maximum of the Q band, which represents to a large degree the energy of the HOMO–LUMO transition. The imine 4 is intrinsically polar due to the asymmetric bridge, and the HOMO is located almost exclusively on the ZnTriPP unit attached to the nitrogen of the imine, and the LUMO on the C-attached ring. Thus the Q-band transition is mapped as a comprehensive charge-transfer from the former ring to the latter. This may have consequences

Smoking is associated with earlier time to revision of total knee arthroplasty.

PubMed

Lim, Chin Tat; Goodman, Stuart B; Huddleston, James I; Harris, Alex H S; Bhowmick, Subhrojyoti; Maloney, William J; Amanatullah, Derek F

2017-10-01

Smoking is associated with early postoperative complications, increased length of hospital stay, and an increased risk of revision after total knee arthroplasty (TKA). However, the effect of smoking on time to revision TKA is unknown. A total of 619 primary TKAs referred to an academic tertiary center for revision TKA were retrospectively stratified according to the patient smoking status. Smoking status was then analyzed for associations with time to revision TKA using a Chi square test. The association was also analyzed according to the indication for revision TKA. Smokers (37/41, 90%) have an increased risk of earlier revision for any reason compared to non-smokers (274/357, 77%, p=0.031). Smokers (37/41, 90%) have an increased risk of earlier revision for any reason compared to ex-smokers (168/221, 76%, p=0.028). Subgroup analysis did not reveal a difference in indication for revision TKA (p>0.05). Smokers are at increased risk of earlier revision TKA when compared to non-smokers and ex-smokers. The risk for ex-smokers was similar to that of non-smokers. Smoking appears to have an all-or-none effect on earlier revision TKA as patients who smoked more did not have higher risk of early revision TKA. These results highlight the need for clinicians to urge patients not to begin smoking and encourage smokers to quit smoking prior to primary TKA. Copyright © 2017 Elsevier B.V. All rights reserved.

Positron lifetime calculation for the elements of the periodic table.

PubMed

Campillo Robles, J M; Ogando, E; Plazaola, F

2007-04-30

Theoretical positron lifetime values have been calculated systematically for most of the elements of the periodic table. Self-consistent and non-self-consistent schemes have been used for the calculation of the electronic structure in the solid, as well as different parametrizations for the positron enhancement factor and correlation energy. The results obtained have been studied and compared with experimental data, confirming the theoretical trends. As is known, positron lifetimes in bulk show a periodic behaviour with atomic number. These calculations also confirm that monovacancy lifetimes follow the same behaviour. The effects of enhancement factors used in calculations have been commented upon. Finally, we have analysed the effects that f and d electrons have on positron lifetimes.

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

NASA Astrophysics Data System (ADS)

Wei, Guangfei; Li, Xiongyao; Wang, Shijie

2015-02-01

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

Floodplains within reservoirs promote earlier spawning of white crappies Pomoxis annularis

USGS Publications Warehouse

Miranda, Leandro E.; Dagel, Jonah D.; Kaczka, Levi J.; Mower, Ethan; Wigen, S. L.

2015-01-01

Reservoirs impounded over floodplain rivers are unique because they may include within their upper reaches extensive shallow water stored over preexistent floodplains. Because of their relatively flat topography and riverine origin, floodplains in the upper reaches of reservoirs provide broad expanses of vegetation within a narrow range of reservoir water levels. Elsewhere in the reservoir, topography creates a band of shallow water along the contour of the reservoir where vegetation often does not grow. Thus, as water levels rise, floodplains may be the first vegetated habitats inundated within the reservoir. We hypothesized that shallow water in reservoir floodplains would attract spawning white crappies Pomoxis annularis earlier than reservoir embayments. Crappie relative abundance over five years in floodplains and embayments of four reservoirs increased as spawning season approached, peaked, and decreased as fish exited shallow water. Relative abundance peaked earlier in floodplains than embayments, and the difference was magnified with higher water levels. Early access to suitable spawning habitat promotes earlier spawning and may increase population fitness. Recognition of the importance of reservoir floodplains, an understanding of how reservoir water levels can be managed to provide timely connectivity to floodplains, and conservation of reservoir floodplains may be focal points of environmental management in reservoirs.

View northeast, wharf A, portion AA, details showing earlier piers ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

View northeast, wharf A, portion AA, details showing earlier piers and braces sloping toward water, reused charred plates for existing decking - U.S. Coast Guard Sandy Hook Station, Western Docking Structure, West of intersection of Canfield Road & Hartshorne Drive, Highlands, Monmouth County, NJ

Theoretical approaches for dynamical ordering of biomolecular systems.

PubMed

Okumura, Hisashi; Higashi, Masahiro; Yoshida, Yuichiro; Sato, Hirofumi; Akiyama, Ryo

2018-02-01

Living systems are characterized by the dynamic assembly and disassembly of biomolecules. The dynamical ordering mechanism of these biomolecules has been investigated both experimentally and theoretically. The main theoretical approaches include quantum mechanical (QM) calculation, all-atom (AA) modeling, and coarse-grained (CG) modeling. The selected approach depends on the size of the target system (which differs among electrons, atoms, molecules, and molecular assemblies). These hierarchal approaches can be combined with molecular dynamics (MD) simulation and/or integral equation theories for liquids, which cover all size hierarchies. We review the framework of quantum mechanical/molecular mechanical (QM/MM) calculations, AA MD simulations, CG modeling, and integral equation theories. Applications of these methods to the dynamical ordering of biomolecular systems are also exemplified. The QM/MM calculation enables the study of chemical reactions. The AA MD simulation, which omits the QM calculation, can follow longer time-scale phenomena. By reducing the number of degrees of freedom and the computational cost, CG modeling can follow much longer time-scale phenomena than AA modeling. Integral equation theories for liquids elucidate the liquid structure, for example, whether the liquid follows a radial distribution function. These theoretical approaches can analyze the dynamic behaviors of biomolecular systems. They also provide useful tools for exploring the dynamic ordering systems of biomolecules, such as self-assembly. This article is part of a Special Issue entitled "Biophysical Exploration of Dynamical Ordering of Biomolecular Systems" edited by Dr. Koichi Kato. Copyright © 2017 Elsevier B.V. All rights reserved.

The calculation of theoretical chromospheric models and the interpretation of the solar spectrum

NASA Technical Reports Server (NTRS)

Avrett, Eugene H.

1994-01-01

Since the early 1970s we have been developing the extensive computer programs needed to construct models of the solar atmosphere and to calculate detailed spectra for use in the interpretation of solar observations. This research involves two major related efforts: work by Avrett and Loeser on the Pandora computer program for non-LTE modeling of the solar atmosphere including a wide range of physical processes, and work by Kurucz on the detailed synthesis of the solar spectrum based on opacity data for over 58 million atomic and molecular lines. Our goals are to determine models of the various features observed on the sun (sunspots, different components of quiet and active regions, and flares) by means of physically realistic models, and to calculate detailed spectra at all wavelengths that match observations of those features. These two goals are interrelated: discrepancies between calculated and observed spectra are used to determine improvements in the structure of the models, and in the detailed physical processes used in both the model calculations and the spectrum calculations. The atmospheric models obtained in this way provide not only the depth variation of various atmospheric parameters, but also a description of the internal physical processes that are responsible for nonradiative heating, and for solar activity in general.

Theoretical calculation of heat of formation and heat of combustion for several flammable gases.

PubMed

Kondo, Shigeo; Takahashi, Akifumi; Tokuhashi, Kazuaki

2002-09-02

Heats of formation have been calculated by the Gaussian-2 (G2) and/or G2MP2 method for a number of flammable gases. As a result, it has been found that the calculated heat of formation for compounds containing, such atoms as fluorine and chlorine tends to deviate from the observed values more than calculations for other molecules do. A simple atom additivity correction (AAC) has been found effective to improve the quality of the heat of formation calculation from the G2 and G2MP2 theories for these molecules. The values of heat of formation thus obtained have been used to calculate the heat of combustion and related constants for evaluating the combustion hazard of flammable gases.

Photodissociation dynamics of nitromethane and methyl nitrite by infrared multiphoton dissociation imaging with quasiclassical trajectory calculations: signatures of the roaming pathway.

PubMed

Dey, Arghya; Fernando, Ravin; Abeysekera, Chamara; Homayoon, Zahra; Bowman, Joel M; Suits, Arthur G

2014-02-07

We combine the techniques of infrared multiphoton dissociation (IRMPD) with state selective ion imaging to probe roaming dynamics in the unimolecular dissociation of nitromethane and methyl nitrite. Recent theoretical calculations suggest a "roaming-mediated isomerization" pathway of nitromethane to methyl nitrite prior to decomposition. State-resolved imaging of the NO product coupled with infrared multiphoton dissociation was carried out to examine this unimolecular decomposition near threshold. The IRMPD images for the NO product from nitromethane are consistent with the earlier IRMPD studies that first suggested the importance of an isomerization pathway. A significant Λ-doublet propensity is seen in nitromethane IRMPD but not methyl nitrite. The experimental observations are augmented by quasiclassical trajectory calculations for nitromethane and methyl nitrite near threshold for each dissociation pathway. The observation of distinct methoxy vibrational excitation for trajectories from nitromethane and methyl nitrite dissociation at the same total energy show that the nitromethane dissociation bears a nonstatistical signature of the roaming isomerization pathway, and this is possibly responsible for the nitromethane Λ-doublet propensity as well.

A preliminary theoretical line-blanketed model solar photosphere

NASA Technical Reports Server (NTRS)

Kurucz, R. L.

1974-01-01

In the theoretical approach to model-atmosphere construction, all opacities are computed theoretically and the temperature-pressure structure is determined by conservation of energy. Until recently, this has not been a very useful method for later type stars, because the line opacity was both poorly known and difficult to calculate. However, methods have now been developed that are capable of representing the line opacity well enough for construction of realistic models. A preliminary theoretical solar model is presented that produces closer agreement with observation than has been heretofore possible. The qualitative advantages and shortcomings of this model are discussued and projected improvements are outlined.

Experimental and theoretical studies of dipole and quadrupole contributions to the vanadium K-edge XANES for VOPO4.2H2O xerogel

NASA Astrophysics Data System (ADS)

Poumellec, B.; Kraizman, V.; Aifa, Y.; Cortès, R.; Novakovich, A.; Vedrinskii, R.

1998-09-01

Angular dependence of the vanadium K-edge x-ray appearance near-edge structure (XANES) for the VOPO4.2H2O xerogel is thoroughly studied both experimentally and theoretically. The main attention is paid to the pre-edge fine structure (PEFS) of the spectra which was shown earlier to be a useful tool for the atomic short order investigations. Good quantitative agreement between theory and experiment obtained for both dipole and quadrupole contributions to the spectra proves validity of the calculation method developed and enables us to ascertain the nature of all the features in the PEFS's. The p-d mixture effect due to distortion of the central coordination octahedron and the quadrupole transitions are proved to be the only mechanisms responsible for the PEFS formation in the case considered. We show that in order to achieve quantitative agreement between experimental and theoretical spectra, it is necessary to include the effect of atomic vibrations, which makes the forbidden transitions to molecular orbitals of the central octahedron (MOCO's) dipole allowed, and to take into account deviation of the crystal layers from the substrate plane, which is not a single crystal but a texture.

Tuning of electronic band gaps and optoelectronic properties of binary strontium chalcogenides by means of doping of magnesium atom(s)- a first principles based theoretical initiative with mBJ, B3LYP and WC-GGA functionals

NASA Astrophysics Data System (ADS)

Debnath, Bimal; Sarkar, Utpal; Debbarma, Manish; Bhattacharjee, Rahul; Chattopadhyaya, Surya

2018-02-01

First principle based theoretical initiative is taken to tune the optoelectronic properties of binary strontium chalcogenide semiconductors by doping magnesium atom(s) into their rock-salt unit cells at specific concentrations x = 0.0, 0.25, 0.50, 0.75 and 1.0 and such tuning is established by studying structural, electronic and optical properties of designed binary compounds and ternary alloys employing WC-GGA, B3LYP and mBJ exchange-correlation functionals. Band structure of each compound is constructed and respective band gaps under all the potential schemes are measured. The band gap bowing and its microscopic origin are calculated using quadratic fit and Zunger's approach, respectively. The atomic and orbital origins of electronic states in the band structure of any compound are explored from its density of states. The nature of chemical bonds between the constituent atoms in each compound is explored from the valence electron density contour plots. Optical properties of any specimen are explored from the computed spectra of its dielectric function, refractive index, extinction coefficient, normal incidence reflectivity, optical conductivity optical absorption and energy loss function. Several calculated results are compared with available experimental and earlier theoretical data.

Theoretical Advanced Study Institute: 2014

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

DeGrand, Thomas

The Theoretical Advanced Study Institute (TASI) was held at the University of Colorado, Boulder, during June 2-27, 2014. The topic was "Journeys through the Precision Frontier: Amplitudes for Colliders." The organizers were Professors Lance Dixon (SLAC) and Frank Petriello (Northwestern and Argonne). There were fifty-one students. Nineteen lecturers gave sixty seventy-five minute lectures. A Proceedings was published. This TASI was unique for its large emphasis on methods for calculating amplitudes. This was embedded in a program describing recent theoretical and phenomenological developments in particle physics. Topics included introductions to the Standard Model, to QCD (both in a collider context andmore » on the lattice), effective field theories, Higgs physics, neutrino interactions, an introduction to experimental techniques, and cosmology.« less

Fine-structure calculations of energy levels, oscillator strengths, and transition probabilities for sulfur-like iron, Fe XI

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

Abou El-Maaref, A., E-mail: aahmh@hotmail.com; Ahmad, Mahmoud; Allam, S.H.

Energy levels, oscillator strengths, and transition probabilities for transitions among the 14 LS states belonging to configurations of sulfur-like iron, Fe XI, have been calculated. These states are represented by configuration interaction wavefunctions and have configurations 3s{sup 2}3p{sup 4}, 3s3p{sup 5}, 3s{sup 2}3p{sup 3}3d, 3s{sup 2}3p{sup 3}4s, 3s{sup 2}3p{sup 3}4p, and 3s{sup 2}3p{sup 3}4d, which give rise to 123 fine-structure energy levels. Extensive configuration interaction calculations using the CIV3 code have been performed. To assess the importance of relativistic effects, the intermediate coupling scheme by means of the Breit–Pauli Hamiltonian terms, such as the one-body mass correction and Darwin term,more » and spin–orbit, spin–other-orbit, and spin–spin corrections, are incorporated within the code. These incorporations adjusted the energy levels, therefore the calculated values are close to the available experimental data. Comparisons between the present calculated energy levels as well as oscillator strengths and both experimental and theoretical data have been performed. Our results show good agreement with earlier works, and they might be useful in thermonuclear fusion research and astrophysical applications. -- Highlights: •Accurate atomic data of iron ions are needed for identification of solar corona. •Extensive configuration interaction wavefunctions including 123 fine-structure levels have been calculated. •The relativistic effects by means of the Breit–Pauli Hamiltonian terms are incorporated. •This incorporation adjusts the energy levels, therefore the calculated values are close to experimental values.« less

Theoretical Noise Analysis on a Position-sensitive Metallic Magnetic Calorimeter

NASA Technical Reports Server (NTRS)

Smith, Stephen J.

2007-01-01

We report on the theoretical noise analysis for a position-sensitive Metallic Magnetic Calorimeter (MMC), consisting of MMC read-out at both ends of a large X-ray absorber. Such devices are under consideration as alternatives to other cryogenic technologies for future X-ray astronomy missions. We use a finite-element model (FEM) to numerically calculate the signal and noise response at the detector outputs and investigate the correlations between the noise measured at each MMC coupled by the absorber. We then calculate, using the optimal filter concept, the theoretical energy and position resolution across the detector and discuss the trade-offs involved in optimizing the detector design for energy resolution, position resolution and count rate. The results show, theoretically, the position-sensitive MMC concept offers impressive spectral and spatial resolving capabilities compared to pixel arrays and similar position-sensitive cryogenic technologies using Transition Edge Sensor (TES) read-out.

Wear Calculation Approach for Sliding - Friction Pairs

NASA Astrophysics Data System (ADS)

Springis, G.; Rudzitis, J.; Lungevics, J.; Berzins, K.

2017-05-01

One of the most important things how to predict the service life of different products is always connected with the choice of adequate method. With the development of production technologies and measuring devices and with ever increasing precision one can get the appropriate data to be used in analytic calculations. Historically one can find several theoretical wear calculation methods but still there are no exact wear calculation model that could be applied to all cases of wear processes because of difficulties connected with a variety of parameters that are involved in wear process of two or several surfaces. Analysing the wear prediction theories that could be classified into definite groups one can state that each of them has shortcomings that might impact the results thus making unnecessary theoretical calculations. The offered wear calculation method is based on the theories of different branches of science. It includes the description of 3D surface micro-topography using standardized roughness parameters, explains the regularities of particle separation from the material in the wear process using fatigue theory and takes into account material’s physical and mechanical characteristics and definite conditions of product’s working time. The proposed wear calculation model could be of value for prediction of the exploitation time for sliding friction pairs thus allowing the best technologies to be chosen for many mechanical details.

Comprehensive methods for earlier detection and monitoring of forest decline

Treesearch

Jennifer Pontius; Richard Hallett

2014-01-01

Forested ecosystems are threatened by invasive pests, pathogens, and unusual climatic events brought about by climate change. Earlier detection of incipient forest health problems and a quantitatively rigorous assessment method is increasingly important. Here, we describe a method that is adaptable across tree species and stress agents and practical for use in the...

Nanoscale thermal transport: Theoretical method and application

NASA Astrophysics Data System (ADS)

Zeng, Yu-Jia; Liu, Yue-Yang; Zhou, Wu-Xing; Chen, Ke-Qiu

2018-03-01

With the size reduction of nanoscale electronic devices, the heat generated by the unit area in integrated circuits will be increasing exponentially, and consequently the thermal management in these devices is a very important issue. In addition, the heat generated by the electronic devices mostly diffuses to the air in the form of waste heat, which makes the thermoelectric energy conversion also an important issue for nowadays. In recent years, the thermal transport properties in nanoscale systems have attracted increasing attention in both experiments and theoretical calculations. In this review, we will discuss various theoretical simulation methods for investigating thermal transport properties and take a glance at several interesting thermal transport phenomena in nanoscale systems. Our emphasizes will lie on the advantage and limitation of calculational method, and the application of nanoscale thermal transport and thermoelectric property. Project supported by the Nation Key Research and Development Program of China (Grant No. 2017YFB0701602) and the National Natural Science Foundation of China (Grant No. 11674092).

Density functional theory calculations of the turbostratically disordered compound [ ( SnSe ) 1 + y ] m ( VSe 2 ) n

DOE PAGES

Rudin, Sven P.; Johnson, David C.

2015-04-30

Among composite materials that layer constituent substances of nanoscale thicknesses, [(SnSe)1+y ]m(VSe2)n emerges as an example where the constituents retain incommensurate lattice structures. Perpendicular to the stacking direction, the system exhibits random translations and random rotations on average, i.e., turbostratic disorder, with local regions showing twelvefold diffraction patterns. Earlier theoretical work on these structures showed that combining density functional theory with an empirical treatment of the van der Waals interaction gave structural parameters in good agreement with experiment, but no attempt was made to examine the relative orientations. Here we approximate the extended system with one extended constituent and onemore » finite constituent, which allows the treatment of all relative orientations on equal footing. Furthermore, the calculations show how the twelvefold periodicity follows from how the ions of the SnSe layer lock in with favored positions relative to the VSe2 layer, and the associated energy scale supports arguments for the overall turbostratic disorder.« less

Atomic calculations for the Fe XX X-ray lines

NASA Technical Reports Server (NTRS)

Mason, H. E.; Bhatia, A. K.

1983-01-01

The atomic data presented here and in Bhatia and Mason (1980) allow the calculation of theoretical intensity ratios for all the EUV, UV, and X-ray lines from Fe XX. Tabulations are presently given for the transitions between levels in the 2s2 2p3, 2s2 2p2 3s, and 2s2 2p2 3d configurations of Fe(19+), and electron collision strengths are calculated by means of the 'distorted wave' approximation. In addition to the theoretical X-ray line intensity ratios, new spectral line identifications from a solar flare are presented.

Earlier Violent Television Exposure and Later Drug Dependence

PubMed Central

Brook, David W.; Katten, Naomi S.; Ning, Yuming; Brook, Judith S.

2013-01-01

This research examined the longitudinal pathways from earlier violent television exposure to later drug dependence. African American and Puerto Rican adolescents were interviewed during three points in time (N = 463). Violent television exposure in late adolescence predicted violent television exposure in young adulthood, which in turn was related to tobacco/marijuana use, nicotine dependence, and later drug dependence. Some policy and clinical implications suggest: a) regulating the times when violent television is broadcast; b) creating developmentally targeted prevention/treatment programs; and c) recognizing that watching violent television may serve as a cue regarding increased susceptibility to nicotine and drug dependence. PMID:18612881

Condensed, solution and gas phase behaviour of mono- and dinuclear 2,6-diacetylpyridine (dap) hydrazone copper complexes probed by X-ray, mass spectrometry and theoretical calculations.

PubMed

Neto, Brenno A D; Viana, Barbara F L; Rodrigues, Thyago S; Lalli, Priscila M; Eberlin, Marcos N; da Silva, Wender A; de Oliveira, Heibbe C B; Gatto, Claudia C

2013-08-28

We describe the synthesis of novel mononuclear and dinuclear copper complexes and an investigation of their behaviour in solution using mass spectrometry (ESI-MS and ESI-MS/MS) and in the solid state using X-ray crystallography. The complexes were synthesized from two widely used diacetylpryridine (dap) ligands, i.e. 2,6-diacetylpyridinebis(benzoic acid hydrazone) and 2,6-diacetylpyridinebis(2-aminobenzoic acid hydrazone). Theoretical calculations (DFT) were used to predict the complex geometries of these new structures, their equilibrium in solution and energies associated with the transformations.

Trend of earlier spring in central Europe continued

NASA Astrophysics Data System (ADS)

Ungersböck, Markus; Jurkovic, Anita; Koch, Elisabeth; Lipa, Wolfgang; Scheifinger, Helfried; Zach-Hermann, Susanne

2013-04-01

Modern phenology is the study of the timing of recurring biological events in the animal and plant world, the causes of their timing with regard to biotic and abiotic forces, and the interrelation among phases of the same or different species. The relationship between phenology and climate explains the importance of plant phenology for Climate Change studies. Plants require light, water, oxygen mineral nutrients and suitable temperature to grow. In temperate zones the seasonal life cycle of plants is primarily controlled by temperature and day length. Higher spring air temperatures are resulting in an earlier onset of the phenological spring in temperate and cool climate. On the other hand changes in phenology due to climate change do have impact on the climate system itself. Vegetation is a dynamic factor in the earth - climate system and has positive and negative feedback mechanisms to the biogeochemical and biogeophysical fluxes to the atmosphere Since the mid of the 1980s spring springs earlier in Europe and autumn is shifting back to the end of the year resulting in a longer vegetation period. The advancement of spring can be clearly attributed to temperature increase in the months prior to leaf unfolding and flowering, the timing of autumn is more complex and cannot easily be attributed to one or some few parameters. To demonstrate that the observed advancement of spring since the mid of 1980s is pro-longed in 2001 to 2010 and the delay of fall and the lengthening of the growing season is confirmed in the last decade we picked out several indicator plants from the PEP725 database www.pep725.eu. The PEP725 database collects data from different European network operators and thus offers a unique compilation of phenological observations; the database is regularly updated. The data follow the same classification scheme, the so called BBCH coding system so they can be compared. Lilac Syringa vulgaris, birch Betula pendula, beech Fagus and horse chestnut Aesculus

Topological Semimetals Studied by Ab Initio Calculations

NASA Astrophysics Data System (ADS)

Hirayama, Motoaki; Okugawa, Ryo; Murakami, Shuichi

2018-04-01

In topological semimetals such as Weyl, Dirac, and nodal-line semimetals, the band gap closes at points or along lines in k space which are not necessarily located at high-symmetry positions in the Brillouin zone. Therefore, it is not straightforward to find these topological semimetals by ab initio calculations because the band structure is usually calculated only along high-symmetry lines. In this paper, we review recent studies on topological semimetals by ab initio calculations. We explain theoretical frameworks which can be used for the search for topological semimetal materials, and some numerical methods used in the ab initio calculations.

Calculation of the dielectric properties of semiconductors

NASA Astrophysics Data System (ADS)

Engel, G. E.; Farid, Behnam

1992-12-01

We report on numerical calculations of the dynamical dielectric function in silicon, using a continued-fraction expansion of the polarizability and a recently proposed representation of the inverse dielectric function in terms of plasmonlike excitations. A number of important technical refinements to further improve the computational efficiency of the method are introduced, making the ab initio calculation of the full energy dependence of the dielectric function comparable in cost to calculation of its static value. Physical results include the observation of previously unresolved features in the random-phase approximated dielectric function and its inverse within the framework of density-functional theory in the local-density approximation, which may be accessible to experiment. We discuss the dispersion of plasmon energies in silicon along the Λ and Δ directions and find improved agreement with experiment compared to earlier calculations. We also present quantitative evidence indicating the degree of violation of the Johnson f-sum rule for the dielectric function due to the nonlocality of the one-electron potential used in the underlying band-structure calculations.

The joint Simon effect: a review and theoretical integration

PubMed Central

Dolk, Thomas; Hommel, Bernhard; Colzato, Lorenza S.; Schütz-Bosbach, Simone; Prinz, Wolfgang; Liepelt, Roman

2014-01-01

The social or joint Simon effect has been developed to investigate how and to what extent people mentally represent their own and other persons' action/task and how these cognitive representations influence an individual's own behavior when interacting with another person. Here, we provide a review of the available evidence and theoretical frameworks. Based on this review, we suggest a comprehensive theory that integrates aspects of earlier approaches–the Referential Coding Account. This account provides an alternative to the social interpretation of the (joint) go-nogo Simon effect (aka the social Simon effect) and is able to integrate seemingly opposite findings on joint action. PMID:25249991

Experimental and theoretical electron-scattering cross-section data for dichloromethane

NASA Astrophysics Data System (ADS)

Krupa, K.; Lange, E.; Blanco, F.; Barbosa, A. S.; Pastega, D. F.; Sanchez, S. d'A.; Bettega, M. H. F.; García, G.; Limão-Vieira, P.; Ferreira da Silva, F.

2018-04-01

We report on a combination of experimental and theoretical investigations into the elastic differential cross sections (DCSs) and integral cross sections for electron interactions with dichloromethane, C H2C l2 , in the incident electron energy over the 7.0-30 eV range. Elastic electron-scattering cross-section calculations have been performed within the framework of the Schwinger multichannel method implemented with pseudopotentials (SMCPP), and the independent-atom model with screening-corrected additivity rule including interference-effects correction (IAM-SCAR+I). The present elastic DCSs have been found to agree reasonably well with the results of IAM-SCAR+I calculations above 20 eV and also with the SMC calculations below 30 eV. Although some discrepancies were found for 7 eV, the agreement between the two theoretical methodologies is remarkable as the electron-impact energy increases. Calculated elastic DCSs are also reported up to 10000 eV for scattering angles from 0° to 180° together with total cross section within the IAM-SCAR+I framework.

Identifying pneumonia outbreaks of public health importance: can emergency department data assist in earlier identification?

PubMed

Hope, Kirsty; Durrheim, David N; Muscatello, David; Merritt, Tony; Zheng, Wei; Massey, Peter; Cashman, Patrick; Eastwood, Keith

2008-08-01

To retrospectively review the performance of a near real-time Emergency Department (ED) Syndromic Surveillance System operating in New South Wales for identifying pneumonia outbreaks of public health importance. Retrospective data was obtained from the NSW Emergency Department data collection for a rural hospital that has experienced a cluster of pneumonia diagnoses among teenage males in August 2006. ED standard reports were examined for signals in the overall count for each respiratory syndrome, and for elevated counts in individual subgroups including; age, sex and admission to hospital status. Using the current thresholds, the ED syndromic surveillance system would have trigged a signal for pneumonia syndrome in children aged 5-16 years four days earlier than the notification by a paediatrician and this signal was maintained for 14 days. If the ED syndromic surveillance system had been operating it could have identified the outbreak earlier than the paediatrician's notification. This may have permitted an earlier public health response. By understanding the behaviour of syndromes during outbreaks of public health importance, response protocols could be developed to facilitate earlier implementation of control measures.

Earlier vegetation green-up has reduced spring dust storms

PubMed Central

Fan, Bihang; Guo, Li; Li, Ning; Chen, Jin; Lin, Henry; Zhang, Xiaoyang; Shen, Miaogen; Rao, Yuhan; Wang, Cong; Ma, Lei

2014-01-01

The observed decline of spring dust storms in Northeast Asia since the 1950s has been attributed to surface wind stilling. However, spring vegetation growth could also restrain dust storms through accumulating aboveground biomass and increasing surface roughness. To investigate the impacts of vegetation spring growth on dust storms, we examine the relationships between recorded spring dust storm outbreaks and satellite-derived vegetation green-up date in Inner Mongolia, Northern China from 1982 to 2008. We find a significant dampening effect of advanced vegetation growth on spring dust storms (r = 0.49, p = 0.01), with a one-day earlier green-up date corresponding to a decrease in annual spring dust storm outbreaks by 3%. Moreover, the higher correlation (r = 0.55, p < 0.01) between green-up date and dust storm outbreak ratio (the ratio of dust storm outbreaks to times of strong wind events) indicates that such effect is independent of changes in surface wind. Spatially, a negative correlation is detected between areas with advanced green-up dates and regional annual spring dust storms (r = −0.49, p = 0.01). This new insight is valuable for understanding dust storms dynamics under the changing climate. Our findings suggest that dust storms in Inner Mongolia will be further mitigated by the projected earlier vegetation green-up in the warming world. PMID:25343265

Changes toward earlier streamflow timing across western North America

USGS Publications Warehouse

Stewart, I.T.; Cayan, D.R.; Dettinger, M.D.

2005-01-01

The highly variable timing of streamflow in snowmelt-dominated basins across western North America is an important consequence, and indicator, of climate fluctuations. Changes in the timing of snowmelt-derived streamflow from 1948 to 2002 were investigated in a network of 302 western North America gauges by examining the center of mass for flow, spring pulse onset dates, and seasonal fractional flows through trend and principal component analyses. Statistical analysis of the streamflow timing measures with Pacific climate indicators identified local and key large-scale processes that govern the regionally coherent parts of the changes and their relative importance. Widespread and regionally coherent trends toward earlier onsets of springtime snowmelt and streamflow have taken place across most of western North America, affecting an area that is much larger than previously recognized. These timing changes have resulted in increasing fractions of annual flow occurring earlier in the water year by 1-4 weeks. The immediate (or proximal) forcings for the spatially coherent parts of the year-to-year fluctuations and longer-term trends of streamflow timing have been higher winter and spring temperatures. Although these temperature changes are partly controlled by the decadal-scale Pacific climate mode [Pacific decadal oscillation (PDO)], a separate and significant part of the variance is associated with a springtime warming trend that spans the PDO phases. ?? 2005 American Meteorological Society.

Earlier vegetation green-up has reduced spring dust storms.

PubMed

Fan, Bihang; Guo, Li; Li, Ning; Chen, Jin; Lin, Henry; Zhang, Xiaoyang; Shen, Miaogen; Rao, Yuhan; Wang, Cong; Ma, Lei

2014-10-24

The observed decline of spring dust storms in Northeast Asia since the 1950s has been attributed to surface wind stilling. However, spring vegetation growth could also restrain dust storms through accumulating aboveground biomass and increasing surface roughness. To investigate the impacts of vegetation spring growth on dust storms, we examine the relationships between recorded spring dust storm outbreaks and satellite-derived vegetation green-up date in Inner Mongolia, Northern China from 1982 to 2008. We find a significant dampening effect of advanced vegetation growth on spring dust storms (r = 0.49, p = 0.01), with a one-day earlier green-up date corresponding to a decrease in annual spring dust storm outbreaks by 3%. Moreover, the higher correlation (r = 0.55, p < 0.01) between green-up date and dust storm outbreak ratio (the ratio of dust storm outbreaks to times of strong wind events) indicates that such effect is independent of changes in surface wind. Spatially, a negative correlation is detected between areas with advanced green-up dates and regional annual spring dust storms (r = -0.49, p = 0.01). This new insight is valuable for understanding dust storms dynamics under the changing climate. Our findings suggest that dust storms in Inner Mongolia will be further mitigated by the projected earlier vegetation green-up in the warming world.

Synthesis, Characterization, and Theoretical Considerations of 1,2-bis(oxyamino)ethane Salts

NASA Technical Reports Server (NTRS)

Crake, Greg; Hawkins, Tom; Hall, Leslie; Tollison, Kerri; Brand, Adam

2003-01-01

The synthesis, characterization, theoretical calculations, and safety studies of energetic salts of 1,2- bis(oxyamino) ethane, (H2N-O-CH2-CH2-O-NH2), were carried out. The salts were characterized by vibrational (infrared, Raman), multinuclear nmr studies (1H, 13C), differential scanning calorimetry (DSC); elemental analysis; and initial safety testing (impact and friction sensitivity) . Theoretical calculations on the neutral, monoprotonated, and doubly protonated species of ethylene bisoxyamine were carried out using xxxx level of theory for the lowest energy structure and these theoretical results compared with the experimentally observed bond distances and vibrational (ir, Raman) frequency values. The single crystal X-ray diffraction study was carried out on the mono-perchlorate salt revealing a high degree of hydrogen bonding with an unexpected structure.

Earlier tachycardia onset in right than left mesial temporal lobe seizures.

PubMed

Kato, Kazuhiro; Jin, Kazutaka; Itabashi, Hisashi; Iwasaki, Masaki; Kakisaka, Yosuke; Aoki, Masashi; Nakasato, Nobukazu

2014-10-07

To clarify whether the presence and timing of peri-ictal heart rate (HR) change is a seizure lateralizing sign in patients with mesial temporal lobe epilepsy (mTLE). Long-term video EEGs were retrospectively reviewed in 21 patients, 7 men and 14 women aged 13 to 67 years, diagnosed as mTLE with MRI lesions in the mesial temporal structures (hippocampal sclerosis in 20 cases, amygdala hypertrophy in 1 case). Seventy-seven partial seizures without secondary generalization were extracted. Peri-ictal HR change was compared between 29 right seizures (9 patients) and 48 left seizures (12 patients). HR abruptly increased in all 29 right seizures and 42 of 48 left seizures. Onset time of HR increase in relation to ictal EEG onset was significantly earlier in right seizures than in left seizures (mean ± SD, -11.5 ± 14.8 vs 9.2 ± 21.7 seconds; p < 0.0001). Time of maximum HR was also significantly earlier in right seizures than in left seizures (36.0 ± 18.1 vs 58.0 ± 28.7 seconds; p < 0.0001). Maximum HR changes from baseline showed no significant difference between right and left seizures (47.5 ± 19.1 vs 40.8 ± 20.0/min). Significantly earlier tachycardia in right than left mTLE seizures supports previous hypotheses that the right cerebral hemisphere is dominant in the sympathetic network. No HR change, or delayed tachycardia possibly due to seizure propagation to the right hemisphere, may be a useful lateralizing sign of left mTLE seizures. © 2014 American Academy of Neurology.

Theoretical calculations of oxygen relaxation in YBa2Cu3O6+x ceramics

NASA Astrophysics Data System (ADS)

Mi, Y.; Schaller, R.; Sathish, S.; Benoit, W.

1991-12-01

A two-dimensional theoretical model of stress-induced point-defect relaxation in a layered structure is presented, with a detailed discussion of the special case of YBa2Cu3O6+x. The experimental results of oxygen relaxation in YBa2Cu3O6+x can be explained qualitatively by this model.

The structure, vibrational spectra and nonlinear optical properties of the L-lysine × tartaric acid complex—Theoretical studies

NASA Astrophysics Data System (ADS)

Drozd, M.; Marchewka, M. K.

2006-05-01

The room temperature X-ray studies of L-lysine × tartaric acid complex are not unambiguous. The disorder of three atoms of carbon in L-lysine molecule is observed. These X-ray studies are ambiguous. The theoretical geometry study performed by DFT methods explain the most doubts which are connected with crystallographic measurements. The theoretical vibrational frequencies and potential energy distribution (PED) of L-lysine × tartaric acid were calculated by B3LYP method. The calculated frequencies were compared with experimental measured IR spectra. The complete assignment of the bands has been made on the basis of the calculated PED. The restricted Hartee-Fock (RHF) methods were used for calculation of the hyperpolarizability for investigated compound. The theoretical results are compared with experimental value of β.

Breaking the theoretical scaling limit for predicting quasiparticle energies: the stochastic GW approach.

PubMed

Neuhauser, Daniel; Gao, Yi; Arntsen, Christopher; Karshenas, Cyrus; Rabani, Eran; Baer, Roi

2014-08-15

We develop a formalism to calculate the quasiparticle energy within the GW many-body perturbation correction to the density functional theory. The occupied and virtual orbitals of the Kohn-Sham Hamiltonian are replaced by stochastic orbitals used to evaluate the Green function G, the polarization potential W, and, thereby, the GW self-energy. The stochastic GW (sGW) formalism relies on novel theoretical concepts such as stochastic time-dependent Hartree propagation, stochastic matrix compression, and spatial or temporal stochastic decoupling techniques. Beyond the theoretical interest, the formalism enables linear scaling GW calculations breaking the theoretical scaling limit for GW as well as circumventing the need for energy cutoff approximations. We illustrate the method for silicon nanocrystals of varying sizes with N_{e}>3000 electrons.

Theoretical studies of solar oscillations

NASA Technical Reports Server (NTRS)

Goldreich, P.

1980-01-01

Possible sources for the excitation of the solar 5 minute oscillations were investigated and a linear non-adiabatic stability code was applied to a preliminary study of the solar g-modes with periods near 160 minutes. Although no definitive conclusions concerning the excitation of these modes were reached, the excitation of the 5 minute oscillations by turbulent stresses in the convection zone remains a viable possibility. Theoretical calculations do not offer much support for the identification of the 160 minute global solar oscillation (reported by several independent observers) as a solar g-mode. A significant advance was made in attempting to reconcile mixing-length theory with the results of the calculations of linearly unstable normal modes. Calculations show that in a convective envelope prepared according to mixing length theory, the only linearly unstable modes are those which correspond to the turbulent eddies which are the basic element of the heuristic mixing length theory.

A theoretical model of job retention for home health care nurses.

PubMed

Ellenbecker, Carol Hall

2004-08-01

Predicted severe nursing shortages and an increasing demand for home health care services have made the retention of experienced, qualified nursing staff a priority for health care organizations. The purpose of this paper is to describe a theoretical model of job retention for home health care nurses. The theoretical model is an integration of the findings of empirical research related to intent to stay and retention, components of Neal's theory of home health care nursing practice and findings from earlier work to develop an instrument to measure home health care nurses' job satisfaction. The theoretical model identifies antecedents to job satisfaction of home health care nurses. The antecedents are intrinsic and extrinsic job characteristics. The model also proposes that job satisfaction is directly related to retention and indirectly related to retention though intent to stay. Individual nurse characteristics are indirectly related to retention through intent to stay. The individual characteristic of tenure is indirectly related to retention through autonomy, as an intrinsic characteristic of job satisfaction, and intent to stay. The proposed model can be used to guide research that explores gaps in knowledge about intent to stay and retention among home health care nurses.

Earlier Mother's Age at Menarche Predicts Rapid Infancy Growth and Childhood Obesity

PubMed Central

Ong, Ken K; Northstone, Kate; Wells, Jonathan CK; Rubin, Carol; Ness, Andy R; Golding, Jean; Dunger, David B

2007-01-01

Background Early menarche tends to be preceded by rapid infancy weight gain and is associated with increased childhood and adult obesity risk. As age at menarche is a heritable trait, we hypothesised that age at menarche in the mother may in turn predict her children's early growth and obesity risk. Methods and Findings We tested associations between mother's age at menarche, mother's adult body size and obesity risk, and her children's growth and obesity risk in 6,009 children from the UK population-based Avon Longitudinal Study of Parents and Children (ALSPAC) birth cohort who had growth and fat mass at age 9 y measured by dual-energy X-ray absorptiometry. A subgroup of 914 children also had detailed infancy and childhood growth data. In the mothers, earlier menarche was associated with shorter adult height (by 0.64 cm/y), increased weight (0.92 kg/y), and body mass index (BMI, 0.51 kg/m2/y; all p < 0.001). In contrast, in her children, earlier mother's menarche predicted taller height at 9 y (by 0.41 cm/y) and greater weight (0.80 kg/y), BMI (0.29 kg/m2/y), and fat mass index (0.22 kg/m2/year; all p < 0.001). Children in the earliest mother's menarche quintile (≤11 y) were more obese than the oldest quintile (≥15 y) (OR, 2.15, 95% CI 1.46 to 3.17; p < 0.001, adjusted for mother's education and BMI). In the subgroup, children in the earliest quintile showed faster gains in weight (p < 0.001) and height (p < 0.001) only from birth to 2 y, but not from 2 to 9 y (p = 0.3–0.8). Conclusions Earlier age at menarche may be a transgenerational marker of a faster growth tempo, characterised by rapid weight gain and growth, particularly during infancy, and leading to taller childhood stature, but likely earlier maturation and therefore shorter adult stature. This growth pattern confers increased childhood and adult obesity risks. PMID:17455989

Theoretical and computational analyses of LNG evaporator

NASA Astrophysics Data System (ADS)

Chidambaram, Palani Kumar; Jo, Yang Myung; Kim, Heuy Dong

2017-04-01

Theoretical and numerical analysis on the fluid flow and heat transfer inside a LNG evaporator is conducted in this work. Methane is used instead of LNG as the operating fluid. This is because; methane constitutes over 80% of natural gas. The analytical calculations are performed using simple mass and energy balance equations. The analytical calculations are made to assess the pressure and temperature variations in the steam tube. Multiphase numerical simulations are performed by solving the governing equations (basic flow equations of continuity, momentum and energy equations) in a portion of the evaporator domain consisting of a single steam pipe. The flow equations are solved along with equations of species transport. Multiphase modeling is incorporated using VOF method. Liquid methane is the primary phase. It vaporizes into the secondary phase gaseous methane. Steam is another secondary phase which flows through the heating coils. Turbulence is modeled by a two equation turbulence model. Both the theoretical and numerical predictions are seen to match well with each other. Further parametric studies are planned based on the current research.

Examinations of electron temperature calculation methods in Thomson scattering diagnostics.

PubMed

Oh, Seungtae; Lee, Jong Ha; Wi, Hanmin

2012-10-01

Electron temperature from Thomson scattering diagnostic is derived through indirect calculation based on theoretical model. χ-square test is commonly used in the calculation, and the reliability of the calculation method highly depends on the noise level of input signals. In the simulations, noise effects of the χ-square test are examined and scale factor test is proposed as an alternative method.

Explicitly-correlated non-born-oppenheimer calculations of the HD molecule in a strong magnetic field

NASA Astrophysics Data System (ADS)

Adamowicz, Ludwik; Stanke, Monika; Tellgren, Erik; Helgaker, Trygve

2017-08-01

Explicitly correlated all-particle Gaussian functions with shifted centers (ECGs) are implemented within the earlier proposed effective variational non-Born-Oppenheimer method for calculating bound states of molecular systems in magnetic field (Adamowicz et al., 2015). The Hamiltonian used in the calculations is obtained by subtracting the operator representing the kinetic energy of the center-of-mass motion from the total laboratory-frame Hamiltonian. Test ECG calculations are performed for the HD molecule.

Non-perturbative background field calculations

NASA Astrophysics Data System (ADS)

Stephens, C. R.

1988-01-01

New methods are developed for calculating one loop functional determinants in quantum field theory. Instead of relying on a calculation of all the eigenvalues of the small fluctuation equation, these techniques exploit the ability of the proper time formalism to reformulate an infinite dimensional field theoretic problem into a finite dimensional covariant quantum mechanical analog, thereby allowing powerful tools such as the method of Jacobi fields to be used advantageously in a field theory setting. More generally the methods developed herein should be extremely valuable when calculating quantum processes in non-constant background fields, offering a utilitarian alternative to the two standard methods of calculation—perturbation theory in the background field or taking the background field into account exactly. The formalism developed also allows for the approximate calculation of covariances of partial differential equations from a knowledge of the solutions of a homogeneous ordinary differential equation.

Theoretical study of the kinetics of chlorine atom abstraction from chloromethanes by atomic chlorine.

PubMed

Brudnik, Katarzyna; Twarda, Maria; Sarzyński, Dariusz; Jodkowski, Jerzy T

2013-10-01

Ab initio calculations at the G3 level were used in a theoretical description of the kinetics and mechanism of the chlorine abstraction reactions from mono-, di-, tri- and tetra-chloromethane by chlorine atoms. The calculated profiles of the potential energy surface of the reaction systems show that the mechanism of the studied reactions is complex and the Cl-abstraction proceeds via the formation of intermediate complexes. The multi-step reaction mechanism consists of two elementary steps in the case of CCl4 + Cl, and three for the other reactions. Rate constants were calculated using the theoretical method based on the RRKM theory and the simplified version of the statistical adiabatic channel model. The temperature dependencies of the calculated rate constants can be expressed, in temperature range of 200-3,000 K as [Formula: see text]. The rate constants for the reverse reactions CH3/CH2Cl/CHCl2/CCl3 + Cl2 were calculated via the equilibrium constants derived theoretically. The kinetic equations [Formula: see text] allow a very good description of the reaction kinetics. The derived expressions are a substantial supplement to the kinetic data necessary to describe and model the complex gas-phase reactions of importance in combustion and atmospheric chemistry.

Calculation and measurement of 144Ce-144Pr β-spectrum

NASA Astrophysics Data System (ADS)

Atroschenko, V.; Kopeikin, V.; Litvinovich, E.; Lukyanchenko, L.; Machulin, I.; Skorokhvatov, M.; Titov, O.

2017-12-01

We calculate beta spectrum of Ce-Pr-144 taking into account several types of corrections. The result is compared with the experimental data obtained at NRC Kurchatov Institute. Using this comparison we estimate the reliability of theoretical calculations for electron and antineutrino spectra from beta decay.

Theoretical study of dissociative recombination of Cl{sub 2}{sup +}

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

Zhang Mingwu; Graduate School of Chinese Academy of Sciences, Beijing 100039; Department of Physics, Stockholm University, S-106 91 Stockholm

Theoretical studies of low-energy electron collisions with Cl{sub 2}{sup +} leading to direct dissociative recombination are presented. The relevant potential energy curves and autoionization widths are calculated by combining electron scattering calculations using the complex Kohn variational method with multireference configuration interaction structure calculations. The dynamics on the four lowest resonant states of all symmetries is studied by the solution of a driven Schroedinger equation. The thermal rate coefficient for dissociative recombination of Cl{sub 2}{sup +} is calculated and the influence on the thermal rate coefficient from vibrational excited target ions is investigated.

Optical properties of B12P2 crystals: Ab initio calculation and EELS

NASA Astrophysics Data System (ADS)

Reshetniak, V. V.; Mavrin, B. N.; Medvedev, V. V.; Perezhogin, I. A.; Kulnitskiy, B. A.

2018-05-01

We report an experimental and theoretical investigation of the electronic structure and optical properties of B12P2 crystals in the energy range up to 60 eV. Experimental studies are performed by the method of electron energy loss spectroscopy, and theoretical studies are carried out using density functional theory and the GW approximation. The calculated dependence of the energy loss function is in agreement with the experiment. Based on the results of the calculations, we determine the optical properties of B12P2 crystals and investigate their anisotropy. The dispersion and density of electronic states are calculated and analyzed.

Quantum chemical calculations of glycine glutaric acid

NASA Astrophysics Data System (ADS)

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

2017-02-01

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

Proposed software system for atomic-structure calculation

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

Fischer, C.F.

1981-07-01

Atomic structure calculations are understood well enough that, at a routine level, an atomic structure software package can be developed. At the Atomic Physics Conference in Riga, 1978 L.V. Chernysheva and M.Y. Amusia of Leningrad University, presented a paper on Software for Atomic Calculations. Their system, called ATOM is based on the Hartree-Fock approximation and correlation is included within the framework of RPAE. Energy level calculations, transition probabilities, photo-ionization cross-sections, electron scattering cross-sections are some of the physical properties that can be evaluated by their system. The MCHF method, together with CI techniques and the Breit-Pauli approximation also provides amore » sound theoretical basis for atomic structure calculations.« less

Discharging patients earlier in the day: a concept worth evaluating.

PubMed

Kravet, Steven J; Levine, Rachel B; Rubin, Haya R; Wright, Scott M

2007-01-01

Patient discharges from the hospital often occur late in the day and are frequently clustered after 4 PM. When inpatients leave earlier in the day, quality is improved because new admissions awaiting beds are able to leave the emergency department sooner and emergency department waiting room backlog is reduced. Nursing staff, whose work patterns traditionally result in high activity of discharge and admission between 5 PM and 8 PM, benefit by spreading out their work across a longer part of the day. Discharging patients earlier in the day also has the potential to increase patient satisfaction. Despite multiple stakeholders in the discharge planning process, physicians play the most important role. Getting physician buy-in requires an ability to teach physicians about the concept of early-in-the-day discharges and their impact on the process. We defined a new physician-centered discharge planning process and introduced it to an internal medicine team with an identical control team as a comparison. Discharge time of day was analyzed for 1 month. Mean time of day of discharge was 13:39 for the intervention group versus 15:45 for the control group (P<.001). If reproduced successfully, this process could improve quality at an important transition point in patient care.

Earlier warning: a multi-indicator approach to monitoring trends in the illicit use of medicines.

PubMed

Mounteney, Jane; Haugland, Siren

2009-03-01

The availability of medicines on the illicit drug market is currently high on the international policy agenda, linked to adverse health consequences including addiction, drug related overdoses and injection related problems. Continuous surveillance of illicit use of medicines allows for earlier identification and reporting of emerging trends and increased possibilities for earlier intervention to prevent spread of use and drug related harm. This paper aims to identify data sources capable of monitoring the illicit use of medicines; present trend findings for Rohypnol and Subutex using a multi-indicator monitoring approach; and consider the relevance of such models for policy makers. Data collection and analysis were undertaken in Bergen, Norway, using the Bergen Earlier Warning System (BEWS), a multi-indicator drug monitoring system. Data were gathered at six monthly intervals from April 2002 to September 2006. Drug indicator data from seizures, treatment, pharmacy sales, helplines, key informants and media monitoring were triangulated and an aggregated differential was used to plot trends. Results for the 4-year period showed a decline in the illicit use of Rohypnol and an increase in the illicit use of Subutex. Multi-indicator surveillance models can play a strategic role in the earlier identification and reporting of emerging trends in illicit use of medicines.

Theoretical and experimental NMR studies on muscimol from fly agaric mushroom (Amanita muscaria)

NASA Astrophysics Data System (ADS)

Kupka, Teobald; Wieczorek, Piotr P.

2016-01-01

In this article we report results of combined theoretical and experimental NMR studies on muscimol, the bioactive alkaloid from fly agaric mushroom (Amanita muscaria). The assignment of 1H and 13C NMR spectra of muscimol in DMSO-d6 was supported by additional two-dimensional heteronuclear correlated spectra (2D NMR) and gauge independent atomic orbital (GIAO) NMR calculations using density functional theory (DFT). The effect of solvent in theoretical calculations was included via polarized continuum model (PCM) and the hybrid three-parameter B3LYP density functional in combination with 6-311++G(3df,2pd) basis set enabled calculation of reliable structures of non-ionized (neutral) molecule and its NH and zwitterionic forms in the gas phase, chloroform, DMSO and water. GIAO NMR calculations, using equilibrium and rovibrationally averaged geometry, at B3LYP/6-31G* and B3LYP/aug-cc-pVTZ-J levels of theory provided muscimol nuclear magnetic shieldings. The theoretical proton and carbon chemical shifts were critically compared with experimental NMR spectra measured in DMSO. Our results provide useful information on its structure in solution. We believe that such data could improve the understanding of basic features of muscimol at atomistic level and provide another tool in studies related to GABA analogs.

Calculating lattice thermal conductivity: a synopsis

NASA Astrophysics Data System (ADS)

Fugallo, Giorgia; Colombo, Luciano

2018-04-01

We provide a tutorial introduction to the modern theoretical and computational schemes available to calculate the lattice thermal conductivity in a crystalline dielectric material. While some important topics in thermal transport will not be covered (including thermal boundary resistance, electronic thermal conduction, and thermal rectification), we aim at: (i) framing the calculation of thermal conductivity within the general non-equilibrium thermodynamics theory of transport coefficients, (ii) presenting the microscopic theory of thermal conduction based on the phonon picture and the Boltzmann transport equation, and (iii) outlining the molecular dynamics schemes to calculate heat transport. A comparative and critical addressing of the merits and drawbacks of each approach will be discussed as well.

Theoretical tuning of the firefly bioluminescence spectra by the modification of oxyluciferin

NASA Astrophysics Data System (ADS)

Cheng, Yuan-Yuan; Zhu, Jia; Liu, Ya-Jun

2014-01-01

Extending the firefly bioluminescence is of practical significance for the improved visualization of living cells and the development of a multicolor reporter. Tuning the color of bioluminescence in fireflies mainly involves the modification of luciferase and luciferin. In this Letter, we theoretically studied the emission spectra of 9 firefly oxyluciferin analogs in the gas phase and in solutions. Three density functionals, including B3LYP, CAM-B3LYP and M06-2X, were employed to theoretically predict the efficiently luminescent analogs. The reliable functionals for calculating the targeted systems were suggested. The luminescence efficiency, solvent effects, and substituent effects are discussed based on the calculated results.

Experimental and theoretical investigation of the temperature dependent electronic quenching of O(1D) atoms in collisions with Kr

NASA Astrophysics Data System (ADS)

Nuñez-Reyes, Dianailys; Kłos, Jacek; Alexander, Millard H.; Dagdigian, Paul J.; Hickson, Kevin M.

2018-03-01

The kinetics and dynamics of the collisional electronic quenching of O(1D) atoms by Kr have been investigated in a joint experimental and theoretical study. The kinetics of quenching were measured over the temperature range 50-296 K using the Laval nozzle method. O(1D) atoms were prepared by 266 nm photolysis of ozone, and the decay of the O(1D) concentration was monitored through vacuum ultraviolet fluorescence at 115.215 nm, from which the rate constant was determined. To interpret the experiments, a quantum close-coupling treatment of the quenching transition from the 1D state to the 3Pj fine-structure levels in collisions with Kr, and also Ar and Xe, was carried out. The relevant potential energy curves and spin-orbit coupling matrix elements were obtained in electronic structure calculations. We find reasonable agreement between computed temperature-dependent O(1D)-Rg (Rg = Ar, Kr, Xe) quenching rate constants and the present measurements for Kr and earlier measurements. In particular, the temperature dependence is well described.

Application of terahertz spectroscopy and theoretical calculation in dimethylurea isomers investigation

NASA Astrophysics Data System (ADS)

Zhao, Yonghong; Li, Zhi; Liu, Jianjun; Chen, Tao; Zhang, Huo; Qin, Binyi; Wu, Yifang

2018-03-01

The characteristic absorption spectra of two structural isomers of dimethylurea(DMU) in 0.6-1.8 THz region have been measured using terahertz time-domain spectroscopy (THZ-TDS) at room temperature. Significant differences have been found between their terahertz spectra and implied that the THZ-TDS is an effective means of identifying structural isomers. To simulate their spectra, calculations on single molecule and cluster of 1,1-DMU and 1,3-DMU were performed, and we found that the cluster calculations using DFT-D3 method are better to predict the experimental spectra. Using the normal mode as displacements in redundant internal coordinates and the GaussView program, most observed THz vibrational modes are assigned to bending and rocking modes related to the intermolecular hydrogen bonding interactions, and twisting mode of ethyl groups. The different spectral features of two isomers mainly arise from different intermolecular hydrogen bonds resulting from different atom arrangements in molecules and different molecule arrangements in crystals. Using the reduced-density-gradient (RDG) analysis, the positions and types of intermolecular hydrogen bonding interactions in 1,1-DMU and 1,3-DMU crystals are visualized. Therefore, we can confirm that THz-TDS can be used as an effective means for the recognition of structural isomers and detection of intermolecular hydrogen bonding interactions in these crystals.

Calculations of unsteady turbulent boundary layers with flow reversal

NASA Technical Reports Server (NTRS)

Nash, J. F.; Patel, V. C.

1975-01-01

The results are presented of a series of computational experiments aimed at studying the characteristics of time-dependent turbulent boundary layers with embedded reversed-flow regions. A calculation method developed earlier was extended to boundary layers with reversed flows for this purpose. The calculations were performed for an idealized family of external velocity distributions, and covered a range of degrees of unsteadiness. The results confirmed those of previous studies in demonstrating that the point of flow reversal is nonsingular in a time-dependent boundary layer. A singularity was observed to develop downstream of reversal, under certain conditions, accompanied by the breakdown of the boundary-layer approximations. A tentative hypothesis was advanced in an attempt to predict the appearance of the singularity, and is shown to be consistent with the calculated results.

Theoretical study of transition-metal ions bound to benzene

NASA Technical Reports Server (NTRS)

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

1992-01-01

Theoretical binding energies are reported for all first-row and selected second-row transition metal ions (M+) bound to benzene. The calculations employ basis sets of at least double-zeta plus polarization quality and account for electron correlation using the modified coupled-pair functional method. While the bending is predominantly electrostatic, the binding energies are significantly increased by electron correlation, because the donation from the metal d orbitals to the benzene pi* orbitals is not well described at the self-consistent-field level. The uncertainties in the computed binding energies are estimated to be about 5 kcal/mol. Although the calculated and experimental binding energies generally agree to within their combined uncertainties, it is likely that the true binding energies lie in the lower portion of the experimental range. This is supported by the very good agreement between the theoretical and recent experimental binding energies for AgC6H6(+).

Traumatic Brain Injury History is Associated with Earlier Age of Onset of Alzheimer Disease

PubMed Central

LoBue, Christian; Wadsworth, Hannah; Wilmoth, Kristin; Clem, Matthew; Hart, John; Womack, Kyle B.; Didehbani, Nyaz; Lacritz, Laura H.; Rossetti, Heidi C.; Cullum, C. Munro

2016-01-01

Objective This study examined whether a history of traumatic brain injury (TBI) is associated with earlier onset of Alzheimer disease (AD), independent of apolipoprotein ε4 status (Apoe4) and gender. Method Participants with a clinical diagnosis of AD (n=7625) were obtained from the National Alzheimer’s Coordinating Center Uniform Data Set, and categorized based on self-reported lifetime TBI with loss of consciousness (LOC) (TBI+ vs TBI-) and presence of Apoe4. ANCOVAs, controlling for gender, race, and education were used to examine the association between history of TBI, presence of Apoe4, and an interaction of both risk factors on estimated age of AD onset. Results Estimated AD onset differed by TBI history and Apoe4 independently (p’s <.001). The TBI+ group had a mean age of onset 2.5 years earlier than the TBI- group. Likewise, Apoe4 carriers had a mean age of onset 2.3 years earlier than non-carriers. While the interaction was non-significant (p = .34), participants having both a history of TBI and Apoe4 had the earliest mean age of onset compared to those with a TBI history or Apoe4 alone (MDifference = 2.8 & 2.7 years, respectively). These results remained unchanged when stratified by gender. Conclusions History of self-reported TBI can be associated with an earlier onset of AD-related cognitive decline, regardless of Apoe4 status and gender. TBI may be related to an underlying neurodegenerative process in AD, but the implications of age at time of injury, severity, and repetitive injuries remain unclear. PMID:27855547

Experimental and theoretical study on Raman spectra of magnesium fluoride clusters and solids.

PubMed

Neelamraju, S; Bach, A; Schön, J C; Fischer, D; Jansen, M

2012-11-21

In this study, the Raman and IR spectra of a large number of isomers of MgF(2) clusters and of possible bulk polymorphs of MgF(2) are calculated and compared with experimental data observed using a low-temperature atom beam deposition. The bulk polymorphs were taken from earlier work, while the cluster modifications for the neutral (MgF(2))(n) (n = 1-10) clusters and charged clusters (up to the trimer anion and cation, (Mg(3)F(7))(-) and (Mg(3)F(5))(+), respectively) are determined in the present work by global energy landscape explorations using simulated annealing. These theoretical calculations are complemented by an experimental study on both the vapor phase and the deposited films of MgF(2), which are generated in a low-temperature atom beam deposition setup for the synthesis of MgF(2) bulk phases. The MgF(2) vapor and film are characterized via Raman spectroscopy of the MgF(2) gas phase species embedded in an Ar-matrix and of the MgF(2)-films deposited onto a cooled substrate, respectively. We find that, in the vapor phase, there are monomers and dimers and charged species to be present in our experimental setup. Furthermore, the results suggest that in the amorphous bulk MgF(2), rutile-like domains are present and MgF(2) clusters similar to those in the matrix. Finally, peaks at about 800 cm(-1), which are in the same range as the A(g) modes of clusters with dangling fluorine atoms connected to three-coordinated Mg atoms, indicate that such dangling bonds are also present in amorphous MgF(2).

Earlier Visual N1 Latencies in Expert Video-Game Players: A Temporal Basis of Enhanced Visuospatial Performance?

PubMed Central

Latham, Andrew J.; Patston, Lucy L. M.; Westermann, Christine; Kirk, Ian J.; Tippett, Lynette J.

2013-01-01

Increasing behavioural evidence suggests that expert video game players (VGPs) show enhanced visual attention and visuospatial abilities, but what underlies these enhancements remains unclear. We administered the Poffenberger paradigm with concurrent electroencephalogram (EEG) recording to assess occipital N1 latencies and interhemispheric transfer time (IHTT) in expert VGPs. Participants comprised 15 right-handed male expert VGPs and 16 non-VGP controls matched for age, handedness, IQ and years of education. Expert VGPs began playing before age 10, had a minimum 8 years experience, and maintained playtime of at least 20 hours per week over the last 6 months. Non-VGPs had little-to-no game play experience (maximum 1.5 years). Participants responded to checkerboard stimuli presented to the left and right visual fields while 128-channel EEG was recorded. Expert VGPs responded significantly more quickly than non-VGPs. Expert VGPs also had significantly earlier occipital N1s in direct visual pathways (the hemisphere contralateral to the visual field in which the stimulus was presented). IHTT was calculated by comparing the latencies of occipital N1 components between hemispheres. No significant between-group differences in electrophysiological estimates of IHTT were found. Shorter N1 latencies may enable expert VGPs to discriminate attended visual stimuli significantly earlier than non-VGPs and contribute to faster responding in visual tasks. As successful video-game play requires precise, time pressured, bimanual motor movements in response to complex visual stimuli, which in this sample began during early childhood, these differences may reflect the experience and training involved during the development of video-game expertise, but training studies are needed to test this prediction. PMID:24058667

Earlier visual N1 latencies in expert video-game players: a temporal basis of enhanced visuospatial performance?

PubMed

Latham, Andrew J; Patston, Lucy L M; Westermann, Christine; Kirk, Ian J; Tippett, Lynette J

2013-01-01

Increasing behavioural evidence suggests that expert video game players (VGPs) show enhanced visual attention and visuospatial abilities, but what underlies these enhancements remains unclear. We administered the Poffenberger paradigm with concurrent electroencephalogram (EEG) recording to assess occipital N1 latencies and interhemispheric transfer time (IHTT) in expert VGPs. Participants comprised 15 right-handed male expert VGPs and 16 non-VGP controls matched for age, handedness, IQ and years of education. Expert VGPs began playing before age 10, had a minimum 8 years experience, and maintained playtime of at least 20 hours per week over the last 6 months. Non-VGPs had little-to-no game play experience (maximum 1.5 years). Participants responded to checkerboard stimuli presented to the left and right visual fields while 128-channel EEG was recorded. Expert VGPs responded significantly more quickly than non-VGPs. Expert VGPs also had significantly earlier occipital N1s in direct visual pathways (the hemisphere contralateral to the visual field in which the stimulus was presented). IHTT was calculated by comparing the latencies of occipital N1 components between hemispheres. No significant between-group differences in electrophysiological estimates of IHTT were found. Shorter N1 latencies may enable expert VGPs to discriminate attended visual stimuli significantly earlier than non-VGPs and contribute to faster responding in visual tasks. As successful video-game play requires precise, time pressured, bimanual motor movements in response to complex visual stimuli, which in this sample began during early childhood, these differences may reflect the experience and training involved during the development of video-game expertise, but training studies are needed to test this prediction.

MHD Energy Bypass Scramjet Performance with Real Gas Effects

NASA Technical Reports Server (NTRS)

Park, Chul; Mehta, Unmeel B.; Bogdanoff, David W.

2000-01-01

The theoretical performance of a scramjet propulsion system incorporating an magneto-hydro-dynamic (MHD) energy bypass scheme is calculated. The one-dimensional analysis developed earlier, in which the theoretical performance is calculated neglecting skin friction and using a sudden-freezing approximation for the nozzle flow, is modified to incorporate the method of Van Driest for turbulent skin friction and a finite-rate chemistry calculation in the nozzle. Unlike in the earlier design, in which four ramp compressions occurred in the pitch plane, in the present design the first two ramp compressions occur in the pitch plane and the next two compressions occur in the yaw plane. The results for the simplified design of a spaceliner show that (1) the present design produces higher specific impulses than the earlier design, (2) skin friction substantially reduces thrust and specific impulse, and (3) the specific impulse of the MHD-bypass system is still better than the non-MHD system and typical rocket over a narrow region of flight speeds and design parameters. Results suggest that the energy management with MHD principles offers the possibility of improving the performance of the scramjet. The technical issues needing further studies are identified.

The molecular structure of 5-X-isatines where (X = F, Cl, and Br) determined by gas-phase electron diffraction with theoretical calculations

NASA Astrophysics Data System (ADS)

Belyakov, Alexander V.; Nikolaenko, Kirill O.; Davidovich, Pavel B.; Ivanov, Anatolii D.; Ponyaev, Alexander I.; Rykov, Anatolii N.; Shishkov, Igor F.

2018-01-01

The molecular structures of 5-X-isatines where X = F (1), Cl (2), and Br (3) were studied by gas-phase electron diffraction (GED) and theoretical calculations at M062X/aug-cc-pVTZ and MP2/aug-cc-pVTZ levels. The best fit of the experimental scattering intensities was obtained for a molecular model of Cs symmetry. The small differences between similar geometric parameters were constrained at the values calculated at the M062X level. The bond distances in the benzene ring are in agreement with their standard values. The (Odbnd)Csbnd C(dbnd O) carbon-carbon bonds of the pyrrole moiety in title compounds (1.581(11), 1.578(8), 1.574(12) Å, respectively) are remarkably lengthened in comparison with standard C(sp2)-C(sp2) value, 1.425(11) Å for N-methylpyrrole. According to NBO analysis this lengthening cannot be attributed to the electrostatic repulsion of oxygen lone pairs alone and is, mainly, due to the hyperconjugation, that is delocalization of oxygen lone pairs of π-type into the corresponding carbon-carbon antibonding orbital, nπ(O)→σ*(Csbnd C). Deletion of σ*(Csbnd C) orbital followed by subsequent geometry optimization led to shortening of the corresponding Csbnd C bond by 0.05-0.06 Å. Electronegative halogen atoms led to increase of Csbnd CXsbnd C endocyclic bond angles at ipso carbon atom as compared with the value of 120° in regular hexagon. According to different aromaticity descriptors, aromaticity of benzene moiety of title compounds is smaller in comparison with benzene molecule. External magnetic field induces diatropic ring current in benzene moiety. Local reactivity descriptors that indicate sites in a molecule that are susceptible to nucleophilic, electrophilic and radical attack are calculated.

A theoretical study of the structure and thermochemical properties of alkali metal fluoroplumbates MPbF3.

PubMed

Boltalin, A I; Korenev, Yu M; Sipachev, V A

2007-07-19

Molecular constants of MPbF3 (M=Li, Na, K, Rb, and Cs) were calculated theoretically at the MP2(full) and B3LYP levels with the SDD (Pb, K, Rb, and Cs) and cc-aug-pVQZ (F, Li, and Na) basis sets to determine the thermochemical characteristics of the substances. Satisfactory agreement with experiment was obtained, including the unexpected nonmonotonic dependence of substance dissociation energies on the alkali metal atomic number. The bond lengths of the theoretical CsPbF3 model were substantially elongated compared with experimental estimates, likely because of errors in both theoretical calculations and electron diffraction data processing.

Colorectal cancer occurs earlier in those exposed to tobacco smoke: implications for screening

PubMed Central

Mahoney, Martin C.; Cummings, K. Michael; Michalek, Arthur M.; Reid, Mary E.; Moysich, Kirsten B.; Hyland, Andrew

2011-01-01

Background Colorectal cancer (CRC) is the third most common cancer in the USA. While various lifestyle factors have been shown to alter the risk for colorectal cancer, recommendations for the early detection of CRC are based only on age and family history. Methods This case-only study examined the age at diagnosis of colorectal cancer in subjects exposed to tobacco smoke. Subjects included all patients who attended RPCI between 1957 and 1997, diagnosed with colorectal cancer, and completed an epidemiologic questionnaire. Adjusted linear regression models were calculated for the various smoking exposures. Results Of the 3,540 cases of colorectal cancer, current smokers demonstrated the youngest age of CRC onset (never: 64.2 vs. current: 57.4, P < 0.001) compared to never smokers, followed by recent former smokers. Among never smokers, individuals with past second-hand smoke exposure were diagnosed at a significantly younger age compared to the unexposed. Conclusion This study found that individuals with heavy, long-term tobacco smoke exposure were significantly younger at the time of CRC diagnosis compared to lifelong never smokers. The implication of this finding is that screening for colorectal cancer, which is recommended to begin at age 50 years for persons at average risk should be initiated 5–10 years earlier for persons with a significant lifetime history of exposure to tobacco smoke. PMID:18264728

The calculation and evaluation for n+54,56,57,58Fe reactions

NASA Astrophysics Data System (ADS)

Han, Yinlu; Xu, Yongli; Guo, Hairui; Zhang, Zhengjun; Liang, Haiying; Cai, Chonghai; Shen, Qingbiao

2017-09-01

All cross sections of neutron-induced reactions, angular distributions, double differential cross sections, angle-integrated spectra, γ-ray production cross sections and energy spectra for 54,56,57,58Fe are calculated by using theoretical models at incident neutron energies from 0.1 to 200 MeV. The present consistent theoretical calculated results are in good agreement with recent experimental data. The present evaluated data are compared with the existing experimental data and evaluated results from ENDF/B-VII, JENDL-4, JEFF-3, and the results are given in ENDF/B format.

Theoretical Studies of Routes to Synthesis of Tetrahedral N4

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Dateo, Christopher E.

2007-01-01

A paper [Chem. Phys. Lett. 345, 295 (2001)] describes theoretical studies of excited electronic states of nitrogen molecules, with a view toward utilizing those states in synthesizing tetrahedral N4, or Td N4 a metastable substance under consideration as a high-energy-density rocket fuel. Several ab initio theoretical approaches were followed in these studies, including complete active space self-consistent field (CASSCF), state-averaged CASSCF (SA-CASSCF), singles configuration interaction (CIS), CIS with second-order and third-order correlation corrections [CIS(D) and CIS(3)], and linear response singles and doubles coupled-cluster (LRCCSD). Standard double zeta polarized and triple zeta double polarized one-particle basis sets were used. The CASSCF calculations overestimated the excitation energies, while SACASSCF calculations partly corrected these overestimates. The accuracy of the CIS calculations varied, depending on the particular state, while the CIS(D), CIS(3), and LRCCSD results were in generally good agreement. The energies of the lowest six excited singlet states of Td N4 as calculated by the LRCCSD were compared with the energies of possible excited states of N2 + N2 fragments, leading to the conclusion that the most likely route for synthesis of Td N4 would involve a combination of two bound quintet states of N2.

O+OH-->O(2)+H: A key reaction for interstellar chemistry. New theoretical results and comparison with experiment.

PubMed

Lique, F; Jorfi, M; Honvault, P; Halvick, P; Lin, S Y; Guo, H; Xie, D Q; Dagdigian, P J; Kłos, J; Alexander, M H

2009-12-14

We report extensive, fully quantum, time-independent (TID) calculations of cross sections at low collision energies and rate constants at low temperatures for the O+OH reaction, of key importance in the production of molecular oxygen in cold, dark, interstellar clouds and in the chemistry of the Earth's atmosphere. Our calculations are compared with TID calculations within the J-shifting approximation, with wave-packet calculations, and with quasiclassical trajectory calculations. The fully quantum TID calculations yield rate constants higher than those from the more approximate methods and are qualitatively consistent with a low-temperature extrapolation of earlier experimental values but not with the most recent experiments at the lowest temperatures.

An experimental and theoretical study of structural damping in compliant foil bearings

NASA Technical Reports Server (NTRS)

Ku, C.-P. Roger

1994-01-01

This paper describes an experimental investigation into the dynamic characteristics of corrugated foil (bump foil) strips used in compliant surface foil bearings. This study provided and opportunity to quantify the structural damping of bump foil strips. The experimental data were compared to results obtained by a theoretical model developed earlier. The effects of bearing design parameters, such as static loads, dynamic displacement amplitudes, bump configurations, pivot locations, surface coatings, and lubricant were also evaluated. An understanding of the dynamic characteristics of bump foil strips resulting from this work offers designers a means for enhancing the design of high-performance compliant foil bearings.

Vibrational spectroscopic studies of Isoleucine by quantum chemical calculations.

PubMed

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

2014-04-24

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

Theoretical and experimental research on laser-beam homogenization based on metal gauze

NASA Astrophysics Data System (ADS)

Liu, Libao; Zhang, Shanshan; Wang, Ling; Zhang, Yanchao; Tian, Zhaoshuo

2018-03-01

Method of homogenization of CO2 laser heating by means of metal gauze is researched theoretically and experimentally. Distribution of light-field of expanded beam passing through metal gauze was numerically calculated with diffractive optical theory and the conclusion is that method is effective, with comparing the results to the situation without metal gauze. Experimentally, using the 30W DC discharge laser as source and enlarging beam by concave lens, with and without metal gauze, beam intensity distributions in thermal paper were compared, meanwhile the experiments based on thermal imager were performed. The experimental result was compatible with theoretical calculation, and all these show that the homogeneity of CO2 laser heating could be enhanced by metal gauze.

Perturbative calculation of two-photon double electron ionization of helium

NASA Astrophysics Data System (ADS)

Ivanov, I. A.; Kheifets, A. S.

2008-05-01

We report the total integrated cross-section (TICS) of two-photon double ionization of helium in the photon energy range from 40 to 54 eV. We compute the TICS in the lowest order perturbation theory (LOPT) using the length and Kramers-Henneberger gauges of the electromagnetic interaction. Our findings indicate that the LOPT gives results for the TICS in agreement with our earlier non-perturbative calculations.

Theoretical studies of spectroscopic problems of importance for atmospheric radiation measurements

NASA Technical Reports Server (NTRS)

Tipping, Richard H.

1994-01-01

Many of the instruments used to deduce the physical parameters of the Earth's atmosphere necessary for climate studies or for pollution monitoring (for instance, temperature versus pressure or number densities of trace molecules) rely on the existence of accurate spectroscopic data and an understanding of the physical processes responsible for the absorption or emission of radiation. During the summer, research was either continued or begun on three distinct problems: (1) an improved theoretical framework for the calculation of the far-wing absorption of allowed spectral lines; (2) a refinement of the calculation of the collision-induced fundamental spectrum of N2; and (3) an investigation of possible line-mixing effects in the fundamental spectrum of CH4. Progress in these three areas is summarized below. During the past few years, we have developed a theoretical framework for the calculation of the absorption of radiation by the far wings of spectral lines. Such absorption due to water vapor plays a crucial role in the greenhouse effect as well as limiting the retrieval of temperature profiles from satellite data. Several improvements in the theory have been made and the results are being prepared for publication. Last year we published results for the theoretical calculation of the absorption of radiation due to the dipoles induced during binary collisions of N2 molecules using independently measured molecular parameters; the results were in reasonable agreement with experimental data. However, recent measurements have revealed new fine structure that has been attributed to line-mixing effects. We do not think that this is correct, rather that the structure results from short-range anisotropic dipoles. We are in the process of including this refinement in our theoretical calculation in order to compare with the new experimental data. Subtle changes in the spectra of CH4 measured by researchers at Langley have also been attributed to line-mixing effects. By

Calculation of Macrosegregation in an Ingot

NASA Technical Reports Server (NTRS)

Poirier, D. R.; Maples, A. L.

1986-01-01

Report describes both two-dimensional theoretical model of macrosegregation (separating into regions of discrete composition) in solidification of binary alloy in chilled rectangular mold and interactive computer program embodying model. Model evolved from previous ones limited to calculating effects of interdendritic fluid flow on final macrosegregation for given input temperature field under assumption of no fluid in bulk melt.

Nonlinear elastic response of strong solids: First-principles calculations of the third-order elastic constants of diamond

DOE PAGES

Hmiel, A.; Winey, J. M.; Gupta, Y. M.; ...

2016-05-23

Accurate theoretical calculations of the nonlinear elastic response of strong solids (e.g., diamond) constitute a fundamental and important scientific need for understanding the response of such materials and for exploring the potential synthesis and design of novel solids. However, without corresponding experimental data, it is difficult to select between predictions from different theoretical methods. Recently the complete set of third-order elastic constants (TOECs) for diamond was determined experimentally, and the validity of various theoretical approaches to calculate the same may now be assessed. We report on the use of density functional theory (DFT) methods to calculate the six third-order elasticmore » constants of diamond. Two different approaches based on homogeneous deformations were used: (1) an energy-strain fitting approach using a prescribed set of deformations, and (2) a longitudinal stress-strain fitting approach using uniaxial compressive strains along the [100], [110], and [111] directions, together with calculated pressure derivatives of the second-order elastic constants. The latter approach provides a direct comparison to the experimental results. The TOECs calculated using the energy-strain approach differ significantly from the measured TOECs. In contrast, calculations using the longitudinal stress-uniaxial strain approach show good agreement with the measured TOECs and match the experimental values significantly better than the TOECs reported in previous theoretical studies. Lastly, our results on diamond have demonstrated that, with proper analysis procedures, first-principles calculations can indeed be used to accurately calculate the TOECs of strong solids.« less

An experimental and theoretical study of reaction mechanisms between nitriles and hydroxylamine.

PubMed

Vörös, Attila; Mucsi, Zoltán; Baán, Zoltán; Timári, Géza; Hermecz, István; Mizsey, Péter; Finta, Zoltán

2014-10-28

The industrially relevant reaction between nitriles and hydroxylamine yielding amidoximes was studied in different molecular solvents and in ionic liquids. In industry, this procedure is carried out on the ton scale in alcohol solutions and the above transformation produces a significant amount of unexpected amide by-product, depending on the nature of the nitrile, which can cause further analytical and purification issues. Although there were earlier attempts to propose mechanisms for this transformation, the real reaction pathway is still under discussion. A new detailed reaction mechanistic explanation, based on theoretical and experimental proof, is given to augment the former mechanisms, which allowed us to find a more efficient, side-product free procedure. Interpreting the theoretical results obtained, it was shown that the application of specific imidazolium, phosphonium and quaternary ammonium based ionic liquids could decrease simultaneously the reaction time while eliminating the amide side-product, leading to the targeted product selectively. This robust and economic procedure now affords a fast, selective amide free synthesis of amidoximes.

Theoretical kinetics study of the F((2)P) + NH3 hydrogen abstraction reaction.

PubMed

Espinosa-Garcia, J; Fernandez-Ramos, A; Suleimanov, Y V; Corchado, J C

2014-01-23

The hydrogen abstraction reaction of fluorine with ammonia represents a true chemical challenge because it is very fast, is followed by secondary abstraction reactions, which are also extremely fast, and presents an experimental/theoretical controversy about rate coefficients. Using a previously developed full-dimensional analytical potential energy surface, we found that the F + NH3 → HF + NH2 system is a barrierless reaction with intermediate complexes in the entry and exit channels. In order to understand the reactivity of the title reaction, thermal rate coefficidents were calculated using two approaches: ring polymer molecular dynamics and quasi-classical trajectory calculations, and these were compared with available experimental data for the common temperature range 276-327 K. The theoretical results obtained show behavior practically independent of temperature, reproducing Walther-Wagner's experiment, but in contrast with Persky's more recent experiment. However, quantitatively, our results are 1 order of magnitude larger than those of Walther-Wagner and reasonably agree with the Persky at the lowest temperature, questioning so Walther-Wagner's older data. At present, the reason for this discrepancy is not clear, although we point out some possible reasons in the light of current theoretical calculations.

Theoretical Accuracy of Along-Track Displacement Measurements from Multiple-Aperture Interferometry (MAI)

PubMed Central

Jung, Hyung-Sup; Lee, Won-Jin; Zhang, Lei

2014-01-01

The measurement of precise along-track displacements has been made with the multiple-aperture interferometry (MAI). The empirical accuracies of the MAI measurements are about 6.3 and 3.57 cm for ERS and ALOS data, respectively. However, the estimated empirical accuracies cannot be generalized to any interferometric pair because they largely depend on the processing parameters and coherence of the used SAR data. A theoretical formula is given to calculate an expected MAI measurement accuracy according to the system and processing parameters and interferometric coherence. In this paper, we have investigated the expected MAI measurement accuracy on the basis of the theoretical formula for the existing X-, C- and L-band satellite SAR systems. The similarity between the expected and empirical MAI measurement accuracies has been tested as well. The expected accuracies of about 2–3 cm and 3–4 cm (γ = 0.8) are calculated for the X- and L-band SAR systems, respectively. For the C-band systems, the expected accuracy of Radarsat-2 ultra-fine is about 3–4 cm and that of Sentinel-1 IW is about 27 cm (γ = 0.8). The results indicate that the expected MAI measurement accuracy of a given interferometric pair can be easily calculated by using the theoretical formula. PMID:25251408

Hydrogen-bonding effect on spin-center transfer of tetrathiafulvalene-linked 6-oxophenalenoxyl evaluated using temperature-dependent cyclic voltammetry and theoretical calculations.

PubMed

Nishida, Shinsuke; Fukui, Kozo; Morita, Yasushi

2014-02-01

The stable tetrathiafulvalene (TTF)-linked 6-oxophenalenoxyl neutral radical exhibits a spin-center transfer with a continuous color change in solution caused by an intramolecular electron transfer, which is dependent on solvent and temperature. Cyclic voltammetry measurements showed that addition of 2,2,2-trifluoroethanol (TFE) to a benzonitrile solution of the neutral radical induces a redox potential shift that is favorable for the spin-center transfer. Temperature-dependent cyclic voltammetry of the neutral radical using a novel low-temperature electrochemical cell demonstrated that the redox potentials change with decreasing temperature in a 199:1 CH2Cl2/TFE mixed solvent. Furthermore, theoretical calculation revealed that the energy levels of the frontier molecular orbitals involved in the spin-center transfer are lowered by the hydrogen-bonding interaction of TFE with the neutral radical. These results indicate that the hydrogen-bonding effect is a key factor for the occurrence of the spin-center transfer of TTF-linked 6-oxophenalenoxyl. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent theoretical progress in top quark pair production at hadron colliders

NASA Astrophysics Data System (ADS)

Mitov, Alexander

2013-05-01

This is a writeup of a plenary talk given at the conference HCP 2012 held November 2012 in Kyoto, Japan. This writeup reviews recent theoretical developments in the following areas of top quark physics at hadron colliders: (a) the forward-backward asymmetry anomaly at the Tevatron, (b) precision top mass determination, (c) state of the art NLO calculations and (d) progress in NNLO calculations.

Calculation of water evapoation in arid climates

USDA-ARS?s Scientific Manuscript database

The concept of maximum rate of water evaporation, i.e., potential evapotranspiration (ETp, mm d-1) was introduced by Charles Thornthwaite in 1944 and defined as the water loss from vegetation with wet soil. Methods to calculate ETp are divided into empirical and theoretical, which combine physical c...

Theoretical calculation of CH3F/N2-broadening coefficients and their temperature dependence

NASA Astrophysics Data System (ADS)

Jellali, C.; Maaroufi, N.; Aroui, H.

2018-07-01

Using Robert and Bonamy formalism (with parabolic and exact trajectories) based on the semi-classical impact theory, N2-broadening coefficients of methyl fluoride CH3F were calculated for transitions belonging to the PP-, PQ-, PR-, RP-, RQ- and RR- sub-branches of the ν6 perpendicular band near 8.5 μm. The calculations showed the predominance of the dipole-quadruple interaction. The J and K rotational quantum numbers dependencies of the computed coefficients that are consistent with previous measurements were clearly observed in this study. For a fixed value of J, we noticed a decrease in the broadening coefficients, which was more significant at lower J values. In order to deduce the temperature exponent, the N2-broadening coefficients of CH3F were calculated at various temperatures of atmospheric interest between 183 and 296 K with J ≤ 60 and K ≤ 10. These exponents were, in general, J-dependent and K-independent, except for K close to J.

Design and theoretical calculation of novel GeSn fully-depleted n-tunneling FET with quantum confinement model for suppression on GIDL effect

NASA Astrophysics Data System (ADS)

Liu, Xiangyu; Hu, Huiyong; Wang, Meng; Miao, Yuanhao; Han, Genquan; Wang, Bin

2018-06-01

In this paper, a novel fully-depleted Ge1-xSnx n-Tunneling FET (FD Ge1-xSnx nTFET) with field plate is investigated theoretically based on the experiment previously published. The energy band structures of Ge1-xSnx are calculated by EMP and the band-to-band tunneling (BTBT) parameters of Ge1-xSnx are calculated by Kane's model. The electrical characteristics of FD Ge1-xSnx nTFET and FD Ge1-xSnx nTFET with field plate (FD-FP Ge1-xSnx nTFET) having various Sn compositions are investigated and simulated with quantum confinement model. The results indicated that the GIDL effect is serious in FD Ge1-xSnx nTFET. By employing the field plate structure, the GIDL effect of FD-FP Ge1-xSnx nTFET is suppressed and the off-state current Ioff is decreased more than 2 orders of magnitude having Sn compositions from 0 to 0.06 compared with FD Ge1-xSnx nTFET. The impact of the difference of work function between field plate metal and channel Φfps is also studied. With the optimized Φfps = 0.0 eV, the on-state current Ion = 4.6 × 10-5 A/μm, the off-state current Ioff = 1.6 × 10-13 A/μm and the maximum on/off ration Ion/Ioff = 2.9 × 108 are achieved.

An earlier age of breast cancer diagnosis related to more frequent use of antiperspirants/deodorants and underarm shaving.

PubMed

McGrath, K G

2003-12-01

Breast cancer incidence suggests a lifestyle cause. A lifestyle factor used near the breast is the application of antiperspirants/deodorants accompanied by axillary shaving. A previous study did not support a link with breast cancer. If these habits have a role in breast cancer development, women using antiperspirants/deodorants and shaving their underarms frequently would be expected to have an earlier age of diagnosis than those doing so less often. An earlier age of diagnosis would also be expected in those starting to use deodorants and shaving at an earlier age. This is the first study to investigate the intensity of underarm exposure in a cohort of breast cancer survivors. Four hundred and thirty-seven females diagnosed with breast cancer were surveyed. Once grouped by their frequency of underarm hygiene habits, the mean age of diagnosis was the primary end point. Secondary end points included the overall frequency of these habits, and potential usage group confounding variables were evaluated. All statistical tests were two-sided. Frequency and earlier onset of antiperspirant/deodorant usage with underarm shaving were associated with an earlier age of breast cancer diagnosis. Combined habits are likely for this earlier age of diagnosis. In conclusion, underarm shaving with antiperspirant/deodorant use may play a role in breast cancer. It is not clear which of these components are involved. Reviewed literature insinuates absorption of aluminium salts facilitated by dermal barrier disruption. Case-controlled investigations are needed before alternative underarm hygiene habits are suggested.

Childhood hair product use and earlier age at menarche in a racially diverse study population: a pilot study.

PubMed

James-Todd, Tamarra; Terry, Mary Beth; Rich-Edwards, Janet; Deierlein, Andrea; Senie, Ruby

2011-06-01

Previous studies suggest that hair products containing endocrine disrupting chemicals could alter puberty. We evaluated the association between childhood hair product use and age at menarche in a racially diverse study population. We recruited 300 African-American, African-Caribbean, Hispanic, and white women from the New York City metropolitan area who were between 18-77 years of age. Data were collected retrospectively on hair oil, lotion, leave-in conditioner, perm, and other types of hair products used before age 13. Recalled age at menarche ranged from 8 to 19 years. We used multivariable binomial regression to evaluate the association between hair product use and age at menarche (<12 vs. ≥12), adjusting for potential confounders. African-Americans were more likely to use hair products and reached menarche earlier than other racial/ethnic groups. Women reporting childhood hair oil use had a risk ratio of 1.4 (95% confidence interval [CI]: 1.1-1.9) for earlier menarche, adjusting for race/ethnicity and year of birth. Hair perm users had an increased risk for earlier menarche (adjusted risk ratio = 1.4, 95% CI: 1.1-1.8). Other types of hair products assessed in this study were not associated with earlier menarche. Childhood hair oil and perm use were associated with earlier menarche. If replicated, these results suggest that hair product use may be important to measure in evaluating earlier age at menarche. Copyright © 2011 Elsevier Inc. All rights reserved.

A theoretical description of the polarization dependence of the sum frequency generation spectroscopy of the water/vapor interface

NASA Astrophysics Data System (ADS)

Perry, Angela; Neipert, Christine; Kasprzyk, Christina Ridley; Green, Tony; Space, Brian; Moore, Preston B.

2005-10-01

An improved time correlation function (TCF) description of sum frequency generation (SFG) spectroscopy was developed and applied to theoretically describing the spectroscopy of the ambient water/vapor interface. A more general TCF expression than was published previously is presented—it is valid over the entire vibrational spectrum for both the real and imaginary parts of the signal. Computationally, earlier time correlation function approaches were limited to short correlation times that made signal processing challenging. Here, this limitation is overcome, and well-averaged spectra are presented for the three independent polarization conditions that are possible for electronically nonresonant SFG. The theoretical spectra compare quite favorably in shape and relative magnitude to extant experimental results in the O H stretching region of water for all polarization geometries. The methodological improvements also allow the calculation of intermolecular SFG spectra. While the intermolecular spectrum of bulk water shows relatively little structure, the interfacial spectra (for polarizations that are sensitive to dipole derivatives normal to the interface—SSP and PPP) show a well-defined intermolecular mode at 875cm-1 that is comparable in intensity to the rest of the intermolecular structure, and has an intensity that is approximately one-sixth of the magnitude of the intense free OH stretching peak. Using instantaneous normal mode methods, the resonance is shown to be due to a wagging mode localized on a single water molecule, almost parallel to the interface, with two hydrogens displaced normal to the interface, and the oxygen anchored in the interface. We have also uncovered the origin of another intermolecular mode at 95cm-1 for the SSP and PPP spectra, and at 220cm-1 for the SPS spectra. These resonances are due to hindered translations perpendicular to the interface for the SSP and PPP spectra, and translations parallel to the interface for the SPS

Comparison of calculations and measurements of neutron leakage from the Little Boy replica

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

Forehand, H.M.; Whalen, P.P.; Malenfant, R.E.

1984-01-01

Measurements of the neutron leakage spectra from 0.6 to 10 MeV are compared with several calculations and earlier measurements of coarse models of Little Boy. Results indicate excellent agreement except at the nose of the device where the neutron exit path is longer, and neutron streaming through geometric discontinuities may present problems. As a result of the agreement, the longstanding difference between calculations and measurements of the Ichiban critical asembly can be resolved: the results reported in 1965 were not correct.

The associations of earlier trauma exposures and history of mental disorders with PTSD after subsequent traumas

PubMed Central

Kessler, Ronald C.; Aguilar-Gaxiola, Sergio; Alonso, Jordi; Bromet, Evelyn J.; Gureje, Oye; Karam, Elie G.; Koenen, Karestan C.; Lee, Sing; Liu, Howard; Pennell, Beth-Ellen; Petukhova, Maria V.; Sampson, Nancy A.; Shahly, Victoria L.; Stein, Dan J.; Atwoli, Lukoye; Borges, Guilherme; Bunting, Brendan; de Girolamo, Giovanni; Gluzman, Semyon; Haro, Josep Maria; Hinkov, Hristo; Kawakami, Norito; Kovess-Masfety, Viviane; Navarro-Mateu, Fernando; Posada-Villa, Jose; Scott, Kate M.; Shalev, Arieh Y.; Have, Margreet ten; Torres, Yolanda; Viana, Maria Carmen; Zaslavsky, Alan M.

2017-01-01

Although earlier trauma exposure is known to predict post-traumatic stress disorder (PTSD) after subsequent traumas, it is unclear if this association is limited to cases where the earlier trauma led to PTSD. Resolution of this uncertainty has important implications for research on pre-trauma vulnerability to PTSD. We examined this issue in the WHO World Mental Health (WMH) Surveys with 34,676 respondents who reported lifetime trauma exposure. One lifetime trauma was selected randomly for each respondent. DSM-IV PTSD due to that trauma was assessed. We reported in a previous paper that four earlier traumas involving interpersonal violence significantly predicted PTSD after subsequent random traumas (OR=1.3–2.5). We also assessed 14 lifetime DSM-IV mood, anxiety, disruptive behavior, and substance disorders prior to random traumas. We show in the current report that only prior anxiety disorders significantly predicted PTSD in a multivariate model (OR=1.5–4.3) and that these disorders interacted significantly with three of the earlier traumas (witnessing atrocities, physical violence victimization, rape). History of witnessing atrocities significantly predicted PTSD after subsequent random traumas only among respondents with prior PTSD (OR=5.6). Histories of physical violence victimization (OR=1.5) and rape after age 17 (OR=17.6) significantly predicted only among respondents with no history of prior anxiety disorders. Although only preliminary due to reliance on retrospective reports, these results suggest that history of anxiety disorders and history of a limited number of earlier traumas might usefully be targeted in future prospective studies as distinct foci of research on individual differences in vulnerability to PTSD after subsequent traumas. PMID:28924183

Theoretical and experimental determination of K - and L -shell x-ray relaxation parameters in Ni

NASA Astrophysics Data System (ADS)

Guerra, M.; Sampaio, J. M.; Parente, F.; Indelicato, P.; Hönicke, P.; Müller, M.; Beckhoff, B.; Marques, J. P.; Santos, J. P.

2018-04-01

Fluorescence yields (FY) for the Ni K and L shells were determined by a theoretical and an experimental group within the framework of the International Initiative on X-ray Fundamental Parameters (FPs) collaboration. Coster-Kronig (CK) parameters were also measured for the L shell of Ni. Theoretical calculations of the same parameters were performed using the Dirac-Fock method, including relativistic and QED corrections. The experimental values for the FY and CK were determined at the PTB laboratory in the synchrotron radiation facility BESSY II, Berlin, Germany, and are compared to the corresponding calculated values.

Diagnosis of varicoceles in men undergoing vasectomy may lead to earlier detection of hypogonadism.

PubMed

Liu, Joceline S; Jones, Madeline; Casey, Jessica T; Fuchs, Amanda B; Cashy, John; Lin, William W

2014-06-01

To determine the temporal relationship between vasectomy, varicocele, and hypogonadism diagnosis. Many young men undergo their first thorough genitourinary examination in their adult lives at the time of vasectomy consultation, providing a unique opportunity for diagnosis of asymptomatic varicoceles. Varicoceles have recently been implicated as a possible reversible contributor to hypogonadism. Hypogonadism may be associated with significant adverse effect, including decreased libido, impaired cognitive function, and increased cardiovascular events. Early diagnosis and treatment of hypogonadism may prevent these adverse sequelae. Data were collected from the Truven Health Analytics MarketScan database, a large outpatient claims database. We reviewed records between 2003 and 2010 for male patients between the ages of 25 and 50 years with International Classification of Diseases, Ninth Revision codes for hypogonadism, vasectomy, and varicocele, and queried dates of first claim. A total of 15,679 men undergoing vasectomies were matched with 156,790 men with nonvasectomy claims in the same year. Vasectomy patients were diagnosed with varicocele at an earlier age (40.9 vs 42.5 years; P=.009). We identified 224,817 men between the ages of 25 and 50 years with a claim of hypogonadism, of which 5883 (2.6%) also had a claim of varicocele. Men with hypogonadism alone were older at presentation compared with men with an accompanying varicocele (41.3 [standard deviation±6.5] vs 34.9 [standard deviation±6.1]; P<.001). Men undergoing vasectomies are diagnosed with varicoceles at a younger age than age-matched controls. Men with varicoceles present with hypogonadism earlier than men without varicoceles. Earlier diagnosis of varicocele at the time of vasectomy allows for earlier detection of hypogonadism. Copyright © 2014 Elsevier Inc. All rights reserved.

Physical and optical properties of DCJTB dye for OLED display applications: Experimental and theoretical investigation

NASA Astrophysics Data System (ADS)

Kurban, Mustafa; Gündüz, Bayram

2017-06-01

In this study, 4-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidin-4-yl-vinyl)-4H-pyran (DCJTB) was achieved using the experimental and theoretical studies. The electronic, optical and spectroscopic properties of DCJTB molecule were first investigated by performing experimental both solution and thin film techniques and then theoretical calculations. Theoretical results showed that one intense electronic transition is 505.26 nm a quite reasonable and agreement with the measured experimental data 505.00 and 503 nm with solution technique and film technique, respectively. Experimental and simple models were also taken into consideration to calculate the optical refractive index (n) of DCJTB molecule. The structural and electronic properties were next calculated using density functional theory (DFT) with B3LYP/6-311G (d, p) basis set. UV, FT-IR spectra characteristics and the electronic properties, such as frontier orbitals, and band gap energy (Eg) of DCJTB were also recorded time-dependent (TD) DFT approach. The theoretical Eg value were found to be 2.269 eV which is consistent with experimental results obtained from solution technique for THF solvent (2.155 eV) and literature (2.16 eV). The results herein obtained reveal that solution is simple, cost-efficient and safe for optoelectronic applications when compared with film technique.

Comparison of experimental surface pressures with theoretical predictions on twin two-dimensional convergent-divergent nozzles

NASA Technical Reports Server (NTRS)

Carlson, J. R.; Pendergraft, O. C., Jr.; Burley, J. R., II

1986-01-01

A three-dimensional subsonic aerodynamic panel code (VSAERO) was used to predict the effects of upper and lower external nozzle flap geometry on the external afterbody/nozzle pressure coefficient distributions and external nozzle drag of nonaxisymmetric convergent-divergent exhaust nozzles having parallel external sidewalls installed on a generic twin-engine high performance aircraft model. Nozzle static pressure coefficient distributions along the upper and lower surfaces near the model centerline and near the outer edges (corner) of the two surfaces were calculated, and nozzle drag was predicted using these surface pressure distributions. A comparison between the theoretical predictions and experimental wind tunnel data is made to evaluate the utility of the code in calculating the flow about these types of non-axisymmetric afterbody configurations. For free-stream Mach numbers of 0.60 and 0.90, the conditions where the flows were attached on the boattails yielded the best comparison between the theoretical predictions and the experimental data. For the Boattail terminal angles of greater than 15 deg., the experimental data for M = 0.60 and 0.90 indicated areas of separated flow, so the theoretical predictions failed to match the experimental data. Even though calculations of regions of separated flows are within the capabilities of the theoretical method, acceptable solutions were not obtained.

Electric dipole moments of the fluorescent probes Prodan and Laurdan: experimental and theoretical evaluations.

PubMed

Vequi-Suplicy, Cíntia C; Coutinho, Kaline; Lamy, M Teresa

2014-03-01

Several experimental and theoretical approaches can be used for a comprehensive understanding of solvent effects on the electronic structure of solutes. In this review, we revisit the influence of solvents on the electronic structure of the fluorescent probes Prodan and Laurdan, focusing on their electric dipole moments. These biologically used probes were synthesized to be sensitive to the environment polarity. However, their solvent-dependent electronic structures are still a matter of discussion in the literature. The absorption and emission spectra of Prodan and Laurdan in different solvents indicate that the two probes have very similar electronic structures in both the ground and excited states. Theoretical calculations confirm that their electronic ground states are very much alike. In this review, we discuss the electric dipole moments of the ground and excited states calculated using the widely applied Lippert-Mataga equation, using both spherical and spheroid prolate cavities for the solute. The dimensions of the cavity were found to be crucial for the calculated dipole moments. These values are compared to those obtained by quantum mechanics calculations, considering Prodan in vacuum, in a polarizable continuum solvent, and using a hybrid quantum mechanics-molecular mechanics methodology. Based on the theoretical approaches it is evident that the Prodan dipole moment can change even in the absence of solute-solvent-specific interactions, which is not taken into consideration with the experimental Lippert-Mataga method. Moreover, in water, for electric dipole moment calculations, it is fundamental to consider hydrogen-bonded molecules.

Theoretical Studies of Liquid He-4 Near the Superfluid Transition

NASA Technical Reports Server (NTRS)

Manousakis, Efstratios

2002-01-01

We performed theoretical studies of liquid helium by applying state of the art simulation and finite-size scaling techniques. We calculated universal scaling functions for the specific heat and superfluid density for various confining geometries relevant for experiments such as the confined helium experiment and other ground based studies. We also studied microscopically how the substrate imposes a boundary condition on the superfluid order parameter as the superfluid film grows layer by layer. Using path-integral Monte Carlo, a quantum Monte Carlo simulation method, we investigated the rich phase diagram of helium monolayer, bilayer and multilayer on a substrate such as graphite. We find excellent agreement with the experimental results using no free parameters. Finally, we carried out preliminary calculations of transport coefficients such as the thermal conductivity for bulk or confined helium systems and of their scaling properties. All our studies provide theoretical support for various experimental studies in microgravity.

Theoretical vibrational spectra of diformates: Diformate anion

NASA Astrophysics Data System (ADS)

Dobrowolski, Jan Cz.; Jamróz, Michał H.; Kazimirski, Jan K.; Bajdor, Krzysztof; Borowiak, Marek A.; Larsson, Ragnar

1999-05-01

The IR spectrum of the most stable diformate anion was calculated at the MP2/6-311++G(3df, 3pd), RHF/6-311++G **, and B3PW91/6-311++G ** levels. The internal coordinates were defined for the diformate anion and used in potential energy distribution (PED) analysis. The PED analysis of the theoretical spectra form the basis for elucidation of the future matrix isolation IR spectra.

Lattice Calculations and the Muon Anomalous Magnetic Moment

NASA Astrophysics Data System (ADS)

Marinković, Marina Krstić

2017-07-01

Anomalous magnetic moment of the muon, a_{μ }=(g_{μ }-2)/2, is one of the most precisely measured quantities in particle physics and it provides a stringent test of the Standard Model. The planned improvements of the experimental precision at Fermilab and at J-PARC propel further reduction of the theoretical uncertainty of a_{μ }. The hope is that the efforts on both sides will help resolve the current discrepancy between the experimental measurement of a_{μ } and its theoretical prediction, and potentially gain insight into new physics. The dominant sources of the uncertainty in the theoretical prediction of a_{μ } are the errors of the hadronic contributions. I will discuss recent progress on determination of hadronic contributions to a_{μ } from lattice calculations.

Photoelectron Angular Distributions of Transition Metal Dioxide Anions - a joint experimental and theoretical study

NASA Astrophysics Data System (ADS)

Iordanov, Ivan; Gunaratne, Dasitha; Harmon, Christopher; Sofo, Jorge; Castleman, A. W., Jr.

2012-02-01

Angular-resolved photoelectron spectroscopy (PES) studies of the MO2- (M=Ti, Zr, Hf, Co, Rh) clusters are presented for the first time along with theoretical calculations of their properties. We confirm previously reported non-angular PES results for the vertical detachment energies (VDE), vibrational energies and geometric structures of these clusters and further explore the effect of the 'lanthanide contraction' on the MO2- clusters by comparing the electronic spectra of 4d and 5d transition metal dioxides. Angular-resolved PES provides the angular momentum contributions to the HOMO of these clusters and we use theoretical calculations to examine the HOMO and compare to our experimental results. First-principles calculations are done using both density functional theory (DFT) and the coupled-cluster, singles, doubles and triples (CCSD(T)) methods.

Compulsive Buying: Earlier Illicit Drug Use, Impulse Buying, Depression, and Adult ADHD Symptoms

PubMed Central

Brook, Judith S.; Zhang, Chenshu; Brook, David W.; Leukefeld, Carl G.

2015-01-01

This longitudinal study examined the association between psychosocial antecedents, including illicit drug use, and adult compulsive buying (CB) across a 29-year time period from mean age 14 to mean age 43. Participants originally came from a community-based random sample of residents in two upstate New York counties. Multivariate linear regression analysis was used to study the relationship between the participant’s earlier psychosocial antecedents and adult CB in the fifth decade of life. The results of the multivariate linear regression analyses showed that gender (female), earlier adult impulse buying (IB), depressive mood, illicit drug use, and concurrent ADHD symptoms were all significantly associated with adult CB at mean age 43. It is important that clinicians treating CB in adults should consider the role of drug use, symptoms of ADHD, IB, depression, and family factors in CB. PMID:26165963

Errors in the Calculation of 27Al Nuclear Magnetic Resonance Chemical Shifts

PubMed Central

Wang, Xianlong; Wang, Chengfei; Zhao, Hui

2012-01-01

Computational chemistry is an important tool for signal assignment of 27Al nuclear magnetic resonance spectra in order to elucidate the species of aluminum(III) in aqueous solutions. The accuracy of the popular theoretical models for computing the 27Al chemical shifts was evaluated by comparing the calculated and experimental chemical shifts in more than one hundred aluminum(III) complexes. In order to differentiate the error due to the chemical shielding tensor calculation from that due to the inadequacy of the molecular geometry prediction, single-crystal X-ray diffraction determined structures were used to build the isolated molecule models for calculating the chemical shifts. The results were compared with those obtained using the calculated geometries at the B3LYP/6-31G(d) level. The isotropic chemical shielding constants computed at different levels have strong linear correlations even though the absolute values differ in tens of ppm. The root-mean-square difference between the experimental chemical shifts and the calculated values is approximately 5 ppm for the calculations based on the X-ray structures, but more than 10 ppm for the calculations based on the computed geometries. The result indicates that the popular theoretical models are adequate in calculating the chemical shifts while an accurate molecular geometry is more critical. PMID:23203134

The structure of geopolymers - Theoretical studies

NASA Astrophysics Data System (ADS)

Koleżyński, Andrzej; Król, Magdalena; Żychowicz, Mikołaj

2018-07-01

This work presents the results of DFT and classical mechanics' calculations and theoretical analysis of geopolymer structure. The calculations were carried out using a bottom-up approach (from small oligomers to clusters with increasing size) for various Si:Al ratio. For all model structures after geometry optimization, respective IR spectra were simulated and compared with the experimental ones. The obtained results show that the concordance of simulated spectra with the experiment, for a given Si:Al ratio, increases with the size of the cluster and increasing local order. Moreover, the increase of the level of local disorder (structure "openness") results in significant band splitting, not observable in real geopolymers. This suggest that, in the case of real geopolymeric structures one can expect the presence of reasonably big, ordered structural fragments, analogous to zeolites.

Reactions of HBO: A Theoretical Study.

DTIC Science & Technology

1987-07-30

8217AO-A163 408 REACTIONS OF HBO: A THEORETICAL STUOY(U) NAYL RESERCH II LAB MASHINGTON DC h PAGE 30 JUL 67 TR-I UNCLRSSIFIED F/G 7/2 MI.mmmhhhh 11111...The transient molecule HBO appears to be an important species. It has only recently been experimentally identified3 . No experimental effort has yet...of HBO are quite fifferent in their approach to the treatment of electron correlation. It is true that both of these calculations use the same finite

Optical graphene quantum dots gas sensors: Theoretical study

NASA Astrophysics Data System (ADS)

Raeyani, D.; Shojaei, S.; Ahmadi-Kandjani, S.

2018-02-01

In this work, we theoretically studied the changes of graphene quantum dots (GQD) absorption spectra under the influence of different gases to indicate optical gas sensing features of GQDs. The adsorption of gas molecules such as CO2, N2 and Ar on GQDs have been theoretically investigated through time-dependent density functional theory (TDDFT) calculations. Our study revealed that UV-Vis absorption spectrum of GQDs in the presence of CO2 undergoes considerable changes than that of N2 and Ar. The shift of maximum absorption wavelength for adsorption of CO2, N2 and Ar in same distance from GQD in addition to density of state (DOS) and orbital analyses have been obtained. To verify our theoretical results, comparison with experimental study has been done and good agreement has been observed. Comparing with electrical property of GQD, optical properties showed an efficient tool to be implemented in gas adsorption and paves the way towards GQD optical gas sensors.

Insight Into Illness and Cognition in Schizophrenia in Earlier and Later Life.

PubMed

Gerretsen, Philip; Voineskos, Aristotle N; Graff-Guerrero, Ariel; Menon, Mahesh; Pollock, Bruce G; Mamo, David C; Mulsant, Benoit H; Rajji, Tarek K

2017-04-01

Impaired insight into illness in schizophrenia is associated with illness severity and deficits in premorbid intellectual function, executive function, and memory. A previous study of patients aged 60 years and older found that illness severity and premorbid intellectual function accounted for variance in insight impairment. As such, we aimed to test whether similar relationships would be observed in earlier life. A retrospective analysis was performed on 1 large sample of participants (n = 171) with a DSM-IV-TR diagnosis of schizophrenia aged 19 to 79 years acquired from 2 studies: (1) a psychosocial intervention trial for older persons with schizophrenia (June 2008 to May 2014) and (2) a diffusion tensor imaging and genetics study of psychosis across the life span (February 2007 to December 2013). We assessed insight into illness using the Positive and Negative Syndrome Scale (PANSS) item G12 and explored its relationship to illness severity (PANSS total modified), premorbid intellectual function (Wechsler Test of Adult Reading [WTAR]), and cognition. Insight impairment was more severe in later life (≥ 60 years) than in earlier years (t = -3.75, P < .001). Across the whole sample, the variance of impaired insight was explained by PANSS total modified (Exp[B] = 1.070, P < .001) and WTAR scores (Exp[B] = 0.970, P = .028). Although age and cognition were correlated with impaired insight, they did not independently contribute to its variance. However, the relationships between impaired insight and illness severity and between impaired insight and cognition, particularly working memory, were stronger in later life than in earlier life. These results suggest an opportunity for intervention may exist with cognitive-enhancing neurostimulation or medications to improve insight into illness in schizophrenia across the life span. Original study registered on ClinicalTrials.gov (identifier: NCT00832845). © Copyright 2017 Physicians Postgraduate Press, Inc.

Characterization of protein folding by a Φ-value calculation with a statistical-mechanical model.

PubMed

Wako, Hiroshi; Abe, Haruo

2016-01-01

The Φ-value analysis approach provides information about transition-state structures along the folding pathway of a protein by measuring the effects of an amino acid mutation on folding kinetics. Here we compared the theoretically calculated Φ values of 27 proteins with their experimentally observed Φ values; the theoretical values were calculated using a simple statistical-mechanical model of protein folding. The theoretically calculated Φ values reflected the corresponding experimentally observed Φ values with reasonable accuracy for many of the proteins, but not for all. The correlation between the theoretically calculated and experimentally observed Φ values strongly depends on whether the protein-folding mechanism assumed in the model holds true in real proteins. In other words, the correlation coefficient can be expected to illuminate the folding mechanisms of proteins, providing the answer to the question of which model more accurately describes protein folding: the framework model or the nucleation-condensation model. In addition, we tried to characterize protein folding with respect to various properties of each protein apart from the size and fold class, such as the free-energy profile, contact-order profile, and sensitivity to the parameters used in the Φ-value calculation. The results showed that any one of these properties alone was not enough to explain protein folding, although each one played a significant role in it. We have confirmed the importance of characterizing protein folding from various perspectives. Our findings have also highlighted that protein folding is highly variable and unique across different proteins, and this should be considered while pursuing a unified theory of protein folding.

Characterization of protein folding by a Φ-value calculation with a statistical-mechanical model

PubMed Central

Wako, Hiroshi; Abe, Haruo

2016-01-01

The Φ-value analysis approach provides information about transition-state structures along the folding pathway of a protein by measuring the effects of an amino acid mutation on folding kinetics. Here we compared the theoretically calculated Φ values of 27 proteins with their experimentally observed Φ values; the theoretical values were calculated using a simple statistical-mechanical model of protein folding. The theoretically calculated Φ values reflected the corresponding experimentally observed Φ values with reasonable accuracy for many of the proteins, but not for all. The correlation between the theoretically calculated and experimentally observed Φ values strongly depends on whether the protein-folding mechanism assumed in the model holds true in real proteins. In other words, the correlation coefficient can be expected to illuminate the folding mechanisms of proteins, providing the answer to the question of which model more accurately describes protein folding: the framework model or the nucleation-condensation model. In addition, we tried to characterize protein folding with respect to various properties of each protein apart from the size and fold class, such as the free-energy profile, contact-order profile, and sensitivity to the parameters used in the Φ-value calculation. The results showed that any one of these properties alone was not enough to explain protein folding, although each one played a significant role in it. We have confirmed the importance of characterizing protein folding from various perspectives. Our findings have also highlighted that protein folding is highly variable and unique across different proteins, and this should be considered while pursuing a unified theory of protein folding. PMID:28409079

An experimental and theoretical analysis of a foil-air bearing rotor system

NASA Astrophysics Data System (ADS)

Bonello, P.; Hassan, M. F. Bin

2018-01-01

Although there is considerable research on the experimental testing of foil-air bearing (FAB) rotor systems, only a small fraction has been correlated with simulations from a full nonlinear model that links the rotor, air film and foil domains, due to modelling complexity and computational burden. An approach for the simultaneous solution of the three domains as a coupled dynamical system, introduced by the first author and adopted by independent researchers, has recently demonstrated its capability to address this problem. This paper uses this approach, with further developments, in an experimental and theoretical study of a FAB-rotor test rig. The test rig is described in detail, including issues with its commissioning. The theoretical analysis uses a recently introduced modal-based bump foil model that accounts for interaction between the bumps and their inertia. The imposition of pressure constraints on the air film is found to delay the predicted onset of instability speed. The results lend experimental validation to a recent theoretically-based claim that the Gümbel condition may not be appropriate for a practical single-pad FAB. The satisfactory prediction of the salient features of the measured nonlinear behavior shows that the air film is indeed highly influential on the response, in contrast to an earlier finding.

The associations of earlier trauma exposures and history of mental disorders with PTSD after subsequent traumas.

PubMed

Kessler, R C; Aguilar-Gaxiola, S; Alonso, J; Bromet, E J; Gureje, O; Karam, E G; Koenen, K C; Lee, S; Liu, H; Pennell, B-E; Petukhova, M V; Sampson, N A; Shahly, V; Stein, D J; Atwoli, L; Borges, G; Bunting, B; de Girolamo, G; Gluzman, S F; Haro, J M; Hinkov, H; Kawakami, N; Kovess-Masfety, V; Navarro-Mateu, F; Posada-Villa, J; Scott, K M; Shalev, A Y; Ten Have, M; Torres, Y; Viana, M C; Zaslavsky, A M

2017-09-19

Although earlier trauma exposure is known to predict posttraumatic stress disorder (PTSD) after subsequent traumas, it is unclear whether this association is limited to cases where the earlier trauma led to PTSD. Resolution of this uncertainty has important implications for research on pretrauma vulnerability to PTSD. We examined this issue in the World Health Organization (WHO) World Mental Health (WMH) Surveys with 34 676 respondents who reported lifetime trauma exposure. One lifetime trauma was selected randomly for each respondent. DSM-IV (Diagnostic and Statistical Manual of Mental Disorders, 4th Edition) PTSD due to that trauma was assessed. We reported in a previous paper that four earlier traumas involving interpersonal violence significantly predicted PTSD after subsequent random traumas (odds ratio (OR)=1.3-2.5). We also assessed 14 lifetime DSM-IV mood, anxiety, disruptive behavior and substance disorders before random traumas. We show in the current report that only prior anxiety disorders significantly predicted PTSD in a multivariate model (OR=1.5-4.3) and that these disorders interacted significantly with three of the earlier traumas (witnessing atrocities, physical violence victimization and rape). History of witnessing atrocities significantly predicted PTSD after subsequent random traumas only among respondents with prior PTSD (OR=5.6). Histories of physical violence victimization (OR=1.5) and rape after age 17 years (OR=17.6) significantly predicted only among respondents with no history of prior anxiety disorders. Although only preliminary due to reliance on retrospective reports, these results suggest that history of anxiety disorders and history of a limited number of earlier traumas might usefully be targeted in future prospective studies as distinct foci of research on individual differences in vulnerability to PTSD after subsequent traumas.Molecular Psychiatry advance online publication, 19 September 2017; doi:10.1038/mp.2017.194.

Theoretical Calculations of Refractive Properties for Hg3Te2Cl2 Crystals

NASA Astrophysics Data System (ADS)

Bokotey, O. V.

2016-05-01

This paper reviews the optical properties, such as refractive index, optical dielectric constant, and reflection coefficient of the Hg3Te2Cl2 crystals. The applications of the Hg3X2Y2 crystals as electronic, optical, and optoelectronic devices are very much determined by the nature and magnitude of these fundamental material properties. The origin of chemical bonding in the crystals is very important for definition of the physical and chemical properties. The main structural feature of the Hg3X2Y2 crystals is the presence of covalent pyramids [XHg3] and linear X-Hg-X groups. Optical properties are calculated according to the model proposed by Harrison. The refractive index in the spectral region far from the absorption edge is determined within the generalized single-oscillator model. The calculated results are found to be in good agreement with experimental data.

Sandia Strehl Calculator Version 1.0

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

Anthony, Stephen M

The Sandia Strehl Calculator is designed to calculate the Gibson and Lanni point spread function (PSF), Strehl ratio, and ensquared energy, allowing non-design immersion, coverslip, and sample layers. It also uses Abbe number calculations to determine the refractive index at specific wavelengths when given the refractive index at a different wavelength and the dispersion. The primary application of Sandia Strehl Calculator is to determine the theoretical impacts of using an optical microscope beyond its normal design parameters. Examples of non-design microscope usage include: a) using coverslips of non-design material b) coverslips of different thicknesses c) imaging deep into an aqueousmore » sample with an immersion objective d) imaging a sample at 37 degrees. All of these changes can affect the imaging quality, sometimes profoundly, but are at the same time non-design conditions employed not infrequently. Rather than having to experimentally determine whether the changes will result in unacceptable image quality, Sandia Strehl Calculator uses existing optical theory to determine the approximate effect of the change, saving the need to perform experiments.« less

Earlier Right Ventricular Pacing in Cardiac Resynchronization Therapy for a Patient with Right Axis Deviation.

PubMed

Hattori, Yusuke; Ishibashi, Kohei; Noda, Takashi; Okamura, Hideo; Kanzaki, Hideaki; Anzai, Toshihisa; Yasuda, Satoshi; Kusano, Kengo

2017-09-01

We describe the case of a 37-year-old woman who presented with complete right bundle branch block and right axis deviation. She was admitted to our hospital due to severe heart failure and was dependent on inotropic agents. Cardiac resynchronization therapy was initiated but did not improve her condition. After the optimization of the pacing timing, we performed earlier right ventricular pacing, which led to an improvement of her heart failure. Earlier right ventricular pacing should be considered in patients with complete right bundle branch block and right axis deviation when cardiac resynchronization therapy is not effective.

Theoretical calculation of electron-positron momentum density in YBa 2Cu 3O 7-δ

NASA Astrophysics Data System (ADS)

Massidda, S.

1990-07-01

We present calculations of the electron-positron momentum density for the high- Tc superconductor YBa 2Cu 3O 7-δ for δ=0 and for the insulating parent compound YBa 2Cu 3O 6, based on first-principle electronic structure calculations performed within the local density approximation (LDA) using the full potential linearized augmented plane wave (FLAPW) method. Our results indicate a small overlap of the positron wave function with the CuO 2 plane electrons and, as a consequence, relatively small signals due to the related Fermi surfaces. By contrast, the present calculations show, after the folding of Umklapp terms according to Lock, Crisp and West, clear Fermi surface breaks arising from the Cu-O chain bands. No general agreement with existing experiments allows a clear definition of Fermi surface structures in the latter. A comparison of the calculated momentum with the experimental two-dimensional angular correlation of annihilation radiation (2D-ACAR) recently measured in Geneva shows an overall agreement for the insulating compound, despite the spurious LDA metallic state, and possibly suggests the importance of O vacancies in experiments performed on non-stoichiometric YBa 2Cu 3O 7-δ samples.

Analysis and calculation of lightning-induced voltages in aircraft electrical circuits

NASA Technical Reports Server (NTRS)

Plumer, J. A.

1974-01-01

Techniques to calculate the transfer functions relating lightning-induced voltages in aircraft electrical circuits to aircraft physical characteristics and lightning current parameters are discussed. The analytical work was carried out concurrently with an experimental program of measurements of lightning-induced voltages in the electrical circuits of an F89-J aircraft. A computer program, ETCAL, developed earlier to calculate resistive and inductive transfer functions is refined to account for skin effect, providing results more valid over a wider range of lightning waveshapes than formerly possible. A computer program, WING, is derived to calculate the resistive and inductive transfer functions between a basic aircraft wing and a circuit conductor inside it. Good agreement is obtained between transfer inductances calculated by WING and those reduced from measured data by ETCAL. This computer program shows promise of expansion to permit eventual calculation of potential lightning-induced voltages in electrical circuits of complete aircraft in the design stage.

Theoretical analysis of three methods for calculating thermal insulation of clothing from thermal manikin.

PubMed

Huang, Jianhua

2012-07-01

There are three methods for calculating thermal insulation of clothing measured with a thermal manikin, i.e. the global method, the serial method, and the parallel method. Under the condition of homogeneous clothing insulation, these three methods yield the same insulation values. If the local heat flux is uniform over the manikin body, the global and serial methods provide the same insulation value. In most cases, the serial method gives a higher insulation value than the global method. There is a possibility that the insulation value from the serial method is lower than the value from the global method. The serial method always gives higher insulation value than the parallel method. The insulation value from the parallel method is higher or lower than the value from the global method, depending on the relationship between the heat loss distribution and the surface temperatures. Under the circumstance of uniform surface temperature distribution over the manikin body, the global and parallel methods give the same insulation value. If the constant surface temperature mode is used in the manikin test, the parallel method can be used to calculate the thermal insulation of clothing. If the constant heat flux mode is used in the manikin test, the serial method can be used to calculate the thermal insulation of clothing. The global method should be used for calculating thermal insulation of clothing for all manikin control modes, especially for thermal comfort regulation mode. The global method should be chosen by clothing manufacturers for labelling their products. The serial and parallel methods provide more information with respect to the different parts of clothing.

A Theoretical Analysis of a New Polarimetric Optical Scheme for Glucose Sensing in the Human Eye

NASA Technical Reports Server (NTRS)

Rovati, Luigi L.; Boeckle, Stefan; Ansari, Rafat R.; Salzman, Jack A. (Technical Monitor)

2002-01-01

The challenging task of in vivo polarimetric glucose sensing is the identification and selection of a scheme to optically access the aqueous humor of the human eye. In this short communication an earlier approach of Cote et al. is theoretically compared with our new optical scheme. Simulations of the new scheme using the eye model of Navarro, suggest that the new optical geometry can overcome the limitations of the previous approach for in vivo measurements of glucose in a human eye.

Compulsive buying: Earlier illicit drug use, impulse buying, depression, and adult ADHD symptoms.

PubMed

Brook, Judith S; Zhang, Chenshu; Brook, David W; Leukefeld, Carl G

2015-08-30

This longitudinal study examined the association between psychosocial antecedents, including illicit drug use, and adult compulsive buying (CB) across a 29-year time period from mean age 14 to mean age 43. Participants originally came from a community-based random sample of residents in two upstate New York counties. Multivariate linear regression analysis was used to study the relationship between the participant's earlier psychosocial antecedents and adult CB in the fifth decade of life. The results of the multivariate linear regression analyses showed that gender (female), earlier adult impulse buying (IB), depressive mood, illicit drug use, and concurrent ADHD symptoms were all significantly associated with adult CB at mean age 43. It is important that clinicians treating CB in adults should consider the role of drug use, symptoms of ADHD, IB, depression, and family factors in CB. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Hybrid density-functional calculations of phonons in LaCoO3

NASA Astrophysics Data System (ADS)

Gryaznov, Denis; Evarestov, Robert A.; Maier, Joachim

2010-12-01

Phonon frequencies at Γ point in nonmagnetic rhombohedral phase of LaCoO3 were calculated using density-functional theory with hybrid exchange correlation functional PBE0. The calculations involved a comparison of results for two types of basis functions commonly used in ab initio calculations, namely, the plane-wave approach and linear combination of atomic orbitals, as implemented in VASP and CRYSTAL computer codes, respectively. A good qualitative, but also within an error margin of less than 30%, a quantitative agreement was observed not only between the two formalisms but also between theoretical and experimental phonon frequency predictions. Moreover, the correlation between the phonon symmetries in cubic and rhombohedral phases is discussed in detail on the basis of group-theoretical analysis. It is concluded that the hybrid PBE0 functional is able to predict correctly the phonon properties in LaCoO3 .

Theoretical model for optical properties of porphyrin

NASA Astrophysics Data System (ADS)

Phan, Anh D.; Nga, Do T.; Phan, The-Long; Thanh, Le T. M.; Anh, Chu T.; Bernad, Sophie; Viet, N. A.

2014-12-01

We propose a simple model to interpret the optical absorption spectra of porphyrin in different solvents. Our model successfully explains the decrease in the intensity of optical absorption at maxima of increased wavelengths. We also prove the dependence of the intensity and peak positions in the absorption spectra on the environment. The nature of the Soret band is supposed to derive from π plasmon. Our theoretical calculations are consistent with previous experimental studies.

Ab initio calculations for the elastic properties of magnesium under pressure

NASA Astrophysics Data System (ADS)

Sin'Ko, G. V.; Smirnov, N. A.

2009-09-01

Results of ab initio calculations of the elastic constants for the hcp, bcc, double hcp (dhcp), and fcc magnesium in a wide range of pressures are presented. The calculated elastic constants are compared with available experimental and theoretical data. We discuss the effect of the electron topological transition that occurs when the hcp structure is compressed on results of calculations and consider possibility of observing the hcp→dhcp transition on the magnesium Hugoniot.

Theoretical Characterizaiton of Visual Signatures

NASA Astrophysics Data System (ADS)

Kashinski, D. O.; Chase, G. M.; di Nallo, O. E.; Scales, A. N.; Vanderley, D. L.; Byrd, E. F. C.

2015-05-01

We are investigating the accuracy of theoretical models used to predict the visible, ultraviolet, and infrared spectra, as well as other properties, of product materials ejected from the muzzle of currently fielded systems. Recent advances in solid propellants has made the management of muzzle signature (flash) a principle issue in weapons development across the calibers. A priori prediction of the electromagnetic spectra of formulations will allow researchers to tailor blends that yield desired signatures and determine spectrographic detection ranges. Quantum chemistry methods at various levels of sophistication have been employed to optimize molecular geometries, compute unscaled vibrational frequencies, and determine the optical spectra of specific gas-phase species. Electronic excitations are being computed using Time Dependent Density Functional Theory (TD-DFT). A full statistical analysis and reliability assessment of computational results is currently underway. A comparison of theoretical results to experimental values found in the literature is used to assess any affects of functional choice and basis set on calculation accuracy. The status of this work will be presented at the conference. Work supported by the ARL, DoD HPCMP, and USMA.

Theoretical and experimental study of fenofibrate and simvastatin

NASA Astrophysics Data System (ADS)

Nicolás Vázquez, Inés; Rodríguez-Núñez, Jesús Rubén; Peña-Caballero, Vicente; Ruvalcaba, Rene Miranda; Aceves-Hernandez, Juan Manuel

2017-12-01

Fenofibrate, an oral fibrate lipid lowering agent, and simvastatin, which reduces plasma levels of low-density lipoprotein cholesterol, are active pharmaceutical ingredients (APIs), currently in the market. We characterized these APIs by thermal analysis and conducted X-ray powder diffraction techniques. Studies should be carried out in the formulation stage before the final composition of a polypill may be established. Thus, it was found in thermochemical studies that both compounds present no chemical interactions in an equimolar mixture of solid samples at room temperature. Theoretical studies were employed to determine possible interactions between fenofibrate and simvastatin. A very weak intramolecular hydrogen bond is formed between the hydroxyl group (O5H5) of the simvastatin with chlorine and carbonyl group (C11O4, C1O2) of the fenofibrate molecule. These weak energy hydrogen bonds have no effect on the chemical stability of the compounds studied. The results were obtained using Density Functional Theory methods; particularly the BPE1BPE and B3LYP functional and 6-31++G** basis set. The values of energy show good approximation when are compared with similar calculations previously reported. Infrared spectra of monomers and dimers were obtained via theoretical calculations.

Earlier versus later continuous Kangaroo Mother Care (KMC) for stable low-birth-weight infants: a randomized controlled trial.

PubMed

Nagai, S; Andrianarimanana, D; Rabesandratana, N; Yonemoto, N; Nakayama, T; Mori, R

2010-06-01

The aim of this study was to examine the effectiveness of earlier continuous Kangaroo Mother Care (KMC) for relatively stable low-birth-weight (LBW) infants in a resource-limited country. A randomized controlled trial was performed in LBW infants at a referral hospital in Madagascar. Earlier continuous KMC (intervention) was begun as soon as possible, within 24 h postbirth, and later continuous KMC (control: conventional care) was begun after complete stabilization (generally after 24 h postbirth). Main outcome measure was mortality during the first 28 days postbirth. This trial was registered with ClinicalTrials.gov, NCT00531492. A total of 73 infants (intervention 37, control 36) were included. Earlier continuous KMC had higher but no statistically different mortality in the first 28 days postbirth (1 vs. 2; risk ratio, 1.95; 95% CIs, 0.18-20.53; p = 1.00). There were no differences in incidence of morbidities. Body weight loss from birth to 24 h postbirth was significantly less in earlier KMC infants compared with later KMC infants. (-34.81 g vs. -73.97 g; mean difference, 39.16 g; 95% CIs, 10.30-68.03; p = 0.01; adjusted p = 0.02). Adverse events and duration of hospitalization were not different between the two groups. Further evaluations of earlier continuous KMC including measurement of KMC dose, are needed in resource-limited countries.

New algorithms for field-theoretic block copolymer simulations: Progress on using adaptive-mesh refinement and sparse matrix solvers in SCFT calculations

NASA Astrophysics Data System (ADS)

Sides, Scott; Jamroz, Ben; Crockett, Robert; Pletzer, Alexander

2012-02-01

Self-consistent field theory (SCFT) for dense polymer melts has been highly successful in describing complex morphologies in block copolymers. Field-theoretic simulations such as these are able to access large length and time scales that are difficult or impossible for particle-based simulations such as molecular dynamics. The modified diffusion equations that arise as a consequence of the coarse-graining procedure in the SCF theory can be efficiently solved with a pseudo-spectral (PS) method that uses fast-Fourier transforms on uniform Cartesian grids. However, PS methods can be difficult to apply in many block copolymer SCFT simulations (eg. confinement, interface adsorption) in which small spatial regions might require finer resolution than most of the simulation grid. Progress on using new solver algorithms to address these problems will be presented. The Tech-X Chompst project aims at marrying the best of adaptive mesh refinement with linear matrix solver algorithms. The Tech-X code PolySwift++ is an SCFT simulation platform that leverages ongoing development in coupling Chombo, a package for solving PDEs via block-structured AMR calculations and embedded boundaries, with PETSc, a toolkit that includes a large assortment of sparse linear solvers.

Molecular structure and conformational composition of 1,3-dihydroxyacetone studied by combined analysis of gas-phase electron diffraction data, rotational constants, and results of theoretical calculations. Ideal gas thermodynamic properties of 1,3-dihydroxyacetone.

PubMed

Dorofeeva, Olga V; Vogt, Natalja; Vogt, Jürgen; Popik, Mikhail V; Rykov, Anatolii N; Vilkov, Lev V

2007-07-19

The molecular structure of 1,3-dihydroxyacetone (DHA) has been studied by gas-phase electron diffraction (GED), combined analysis of GED and microwave (MW) data, ab initio, and density functional theory calculations. The equilibrium re structure of DHA was determined by a joint analysis of the GED data and rotational constants taken from the literature. The anharmonic vibrational corrections to the internuclear distances (re-ra) and to the rotational constants (B(i)e-B(i)0) needed for the estimation of the re structure were calculated from the B3LYP/cc-pVTZ cubic force field. It was found that the experimental data are well reproduced by assuming that DHA consists of a mixture of three conformers. The most stable conformer of C2v symmetry has two hydrogen bonds, whereas the next two lowest energy conformers (Cs and C1 symmetry) have one hydrogen bond and their abundance is about 30% in total. A combined analysis of GED and MW data led to the following equilibrium structural parameters (re) of the most abundant conformer of DHA (the uncertainties in parentheses are 3 times the standard deviations): r(C=O)=1.215(2) A, r(C-C)=1.516(2) A, r(C-O)=1.393(2) A, r(C-H)=1.096(4) A, r(O-H)=0.967(4) A, angleC-C=O=119.9(2) degrees, angleC-C-O=111.0(2) degrees, angleC-C-H=108.2(7) degrees, angleC-O-H=106.5(7) degrees. These structural parameters reproduce the experimental B(i)0 values within 0.05 MHz. The experimental structural parameters are in good agreement with those obtained from theoretical calculations. Ideal gas thermodynamic functions (S degrees (T), C degrees p(T), and H degrees (T)-H degrees (0)) of DHA were calculated on the basis of experimental and theoretical molecular parameters obtained in this work. The enthalpy of formation of DHA, -523+/-4 kJ/mol, was calculated by the atomization procedure using the G3X method.

Linear Scaling Density Functional Calculations with Gaussian Orbitals

NASA Technical Reports Server (NTRS)

Scuseria, Gustavo E.

1999-01-01

Recent advances in linear scaling algorithms that circumvent the computational bottlenecks of large-scale electronic structure simulations make it possible to carry out density functional calculations with Gaussian orbitals on molecules containing more than 1000 atoms and 15000 basis functions using current workstations and personal computers. This paper discusses the recent theoretical developments that have led to these advances and demonstrates in a series of benchmark calculations the present capabilities of state-of-the-art computational quantum chemistry programs for the prediction of molecular structure and properties.

A theoretical study of the electronic transition moment for the C2 Swan band system

NASA Technical Reports Server (NTRS)

Arnold, J. O.; Langhoff, S. R.

1978-01-01

Large-scale self-consistent-field plus configuration-interaction calculations have been performed for the a 3Pi u and d 3Pi g states of C2. The theoretical potential curves are in good agreement with those found by a Klein-Dunham analysis of measured molecular constants in terms of shape and excitation energy. The sum of the squares of the theoretical transition moments between the states at 2.44 bohr is 4.12 a.u. which agrees with the results of shock tube measurements. The variation in the sum of the squares of the theoretical moments with internuclear separation agrees with the values of Danylewych and Nicholls (1974). Based on the data for C2 and mother molecules, it is suggested that CI calculations using near Hartree-Fock quality Slater basis sets produce highly reliable transition moments.

An assessment of some theoretical models used for the calculation of the refractive index of InXGa1-xAs

NASA Astrophysics Data System (ADS)

Engelbrecht, J. A. A.

2018-04-01

Theoretical models used for the determination of the refractive index of InXGa1-XAs are reviewed and compared. Attention is drawn to some problems experienced with some of the models. Models also extended to the mid-infrared region of the electromagnetic spectrum. Theoretical results in the mid-infrared region are then compared to previously published experimental results.

Theoretical model for plasmonic photothermal response of gold nanostructures solutions

NASA Astrophysics Data System (ADS)

Phan, Anh D.; Nga, Do T.; Viet, Nguyen A.

2018-03-01

Photothermal effects of gold core-shell nanoparticles and nanorods dispersed in water are theoretically investigated using the transient bioheat equation and the extended Mie theory. Properly calculating the absorption cross section is an extremely crucial milestone to determine the elevation of solution temperature. The nanostructures are assumed to be randomly and uniformly distributed in the solution. Compared to previous experiments, our theoretical temperature increase during laser light illumination provides, in various systems, both reasonable qualitative and quantitative agreement. This approach can be a highly reliable tool to predict photothermal effects in experimentally unexplored structures. We also validate our approach and discuss itslimitations.

BH-DFTB/DFT calculations for iron clusters

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

Aktürk, Abdurrahman; Sebetci, Ali, E-mail: asebetci@mevlana.edu.tr

2016-05-15

We present a study on the structural, electronic, and magnetic properties of Fe{sub n}(n  =  2  −  20) clusters by performing density functional tight binding (DFTB) calculations within a basin hopping (BH) global optimization search followed by density functional theory (DFT) investigations. The structures, total energies and total spin magnetic moments are calculated and compared with previously reported theoretical and experimental results. Two basis sets SDD with ECP and 6-31G** are employed in the DFT calculations together with BLYP GGA exchange-correlation functional. The results indicate that the offered BH-DFTB/DFT strategy collects all the global minima of which different minima havemore » been reported in the previous studies by different groups. Small Fe clusters have three kinds of packing; icosahedral (Fe{sub 9−13}), centered hexagonal antiprism (Fe{sub 14−17}, Fe{sub 20}), and truncated decahedral (Fe{sub 17(2)}, Fe{sub 18−19}). It is obtained in a qualitative agreement with the time of flight mass spectra that the magic numbers for the small Fe clusters are 7, 13, 15, and 19 and with the collision induced dissociation experiments that the sizes 6, 7, 13, 15, and 19 are thermodynamically more stable than their neighboring sizes. The spin magnetic moment per atom of Fe{sub n}(n = 2 − 20) clusters is between 2.4 and 3.6 μ{sub B} for the most of the sizes. The antiferromagnetic coupling between the central and the surface atoms of the Fe{sub 13} icosahedron, which have already been reported by experimental and theoretical studies, is verified by our calculations as well. The quantitative disagreements between the calculations and measurements of the magnetic moments of the individual sizes are still to be resolved.« less

Theoretical calculation of enthalpy of formation of multiconformational molecules: 1,2-ethanediol, propanediols, and glycerol

NASA Astrophysics Data System (ADS)

Dorofeeva, Olga V.; Suchkova, Taisiya A.

2018-04-01

The gas-phase enthalpies of formation of four molecules with high flexibility, which leads to the existence of a large number of low-energy conformers, were calculated with the G4 method to see whether the lowest energy conformer is sufficient to achieve high accuracy in the computed values. The calculated values were in good agreement with the experiment, whereas adding the correction for conformer distribution makes the agreement worse. The reason for this effect is a large anharmonicity of low-frequency torsional motions, which is ignored in the calculation of ZPVE and thermal enthalpy. It was shown that the approximate correction for anharmonicity estimated using a free rotor model is of very similar magnitude compared with the conformer correction but has the opposite sign, and thus almost fully compensates for it. Therefore, the common practice of adding only the conformer correction is not without problems.

The calculation of theoretical chromospheric models and the interpretation of solar spectra from rockets and spacecraft

NASA Technical Reports Server (NTRS)

Avrett, Eugene H.

1993-01-01

Since the early 1970s we have been developing the extensive computer programs needed to construct models of the solar atmosphere and to calculate detailed spectra for use in the interpretation of solar observations. This research involves two major related efforts: work by Avrett and Loeser on the Pandora computer program for non-LTE modeling of the solar atmosphere including a wide range of physical processes, and work by Kurucz on the detailed synthesis of the solar spectrum based on opacity data for over 58 million atomic and molecular lines. Our goals are to determine models of the various features observed on the Sun (sunspots, different components of quiet and active regions, and flares) by means of physically realistic models, and to calculate detailed spectra at all wavelengths that match observations of those features. These two goals are interrelated: discrepancies between calculated and observed spectra are used to determine improvements in the structure of the models, and in the detailed physical processes used in both the model calculations and the spectrum calculations. The atmospheric models obtained in this way provide not only the depth variation of various atmospheric parameters, but also a description of the internal physical processes that are responsible for non-radiative heating, and for solar activity in general.

A quantum theoretical study of polyimides

NASA Technical Reports Server (NTRS)

Burke, Luke A.

1987-01-01

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

a Protocol for High-Accuracy Theoretical Thermochemistry

NASA Astrophysics Data System (ADS)

Welch, Bradley; Dawes, Richard

2017-06-01

Theoretical studies of spectroscopy and reaction dynamics including the necessary development of potential energy surfaces rely on accurate thermochemical information. The Active Thermochemical Tables (ATcT) approach by Ruscic^{1} incorporates data for a large number of chemical species from a variety of sources (both experimental and theoretical) and derives a self-consistent network capable of making extremely accurate estimates of quantities such as temperature dependent enthalpies of formation. The network provides rigorous uncertainties, and since the values don't rely on a single measurement or calculation, the provenance of each quantity is also obtained. To expand and improve the network it is desirable to have a reliable protocol such as the HEAT approach^{2} for calculating accurate theoretical data. Here we present and benchmark an approach based on explicitly-correlated coupled-cluster theory and vibrational perturbation theory (VPT2). Methyldioxy and Methyl Hydroperoxide are important and well-characterized species in combustion processes and begin the family of (ethyl-, propyl-based, etc) similar compounds (much less is known about the larger members). Accurate anharmonic frequencies are essential to accurately describe even the 0 K enthalpies of formation, but are especially important for finite temperature studies. Here we benchmark the spectroscopic and thermochemical accuracy of the approach, comparing with available data for the smallest systems, and comment on the outlook for larger systems that are less well-known and characterized. ^{1}B. Ruscic, Active Thermochemical Tables (ATcT) values based on ver. 1.118 of the Thermochemical Network (2015); available at ATcT.anl.gov ^{2}A. Tajti, P. G. Szalay, A. G. Császár, M. Kállay, J. Gauss, E. F. Valeev, B. A. Flowers, J. Vázquez, and J. F. Stanton. JCP 121, (2004): 11599.

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

NASA Astrophysics Data System (ADS)

Moosavi-Tekyeh, Zainab; Dastani, Najmeh

2015-12-01

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

Comparison of experimental with theoretical total-pressure loss in parallel-walled turbojet combustors

NASA Technical Reports Server (NTRS)

Dittrich, Ralph T

1957-01-01

An experimental investigation of combustor total-pressure loss was undertaken to confirm previous theoretical analyses of effects of geometric and flow variables and of heat addition. The results indicate that a reasonable estimate of cold-flow total-pressure-loss coefficient may be obtained from the theoretical analyses. Calculated total-pressure loss due to heat addition agreed with experimental data only when there was no flame ejection from the liner at the upstream air-entry holes.

Recent advances in jointed quantum mechanics and molecular mechanics calculations of biological macromolecules: schemes and applications coupled to ab initio calculations.

PubMed

Hagiwara, Yohsuke; Tateno, Masaru

2010-10-20

We review the recent research on the functional mechanisms of biological macromolecules using theoretical methodologies coupled to ab initio quantum mechanical (QM) treatments of reaction centers in proteins and nucleic acids. Since in most cases such biological molecules are large, the computational costs of performing ab initio calculations for the entire structures are prohibitive. Instead, simulations that are jointed with molecular mechanics (MM) calculations are crucial to evaluate the long-range electrostatic interactions, which significantly affect the electronic structures of biological macromolecules. Thus, we focus our attention on the methodologies/schemes and applications of jointed QM/MM calculations, and discuss the critical issues to be elucidated in biological macromolecular systems. © 2010 IOP Publishing Ltd

Statistical Issues for Calculating Reentry Hazards

NASA Technical Reports Server (NTRS)

Matney, Mark; Bacon, John

2016-01-01

A number of statistical tools have been developed over the years for assessing the risk of reentering object to human populations. These tools make use of the characteristics (e.g., mass, shape, size) of debris that are predicted by aerothermal models to survive reentry. This information, combined with information on the expected ground path of the reentry, is used to compute the probability that one or more of the surviving debris might hit a person on the ground and cause one or more casualties. The statistical portion of this analysis relies on a number of assumptions about how the debris footprint and the human population are distributed in latitude and longitude, and how to use that information to arrive at realistic risk numbers. This inevitably involves assumptions that simplify the problem and make it tractable, but it is often difficult to test the accuracy and applicability of these assumptions. This paper builds on previous IAASS work to re-examine many of these theoretical assumptions, including the mathematical basis for the hazard calculations, and outlining the conditions under which the simplifying assumptions hold. This study also employs empirical and theoretical information to test these assumptions, and makes recommendations how to improve the accuracy of these calculations in the future.

Theoretical Studies on InGaAs/InAlAs SAGCM Avalanche Photodiodes

NASA Astrophysics Data System (ADS)

Cao, Siyu; Zhao, Yue; ur Rehman, Sajid; Feng, Shuai; Zuo, Yuhua; Li, Chuanbo; Zhang, Lichun; Cheng, Buwen; Wang, Qiming

2018-05-01

In this paper, we provide a detailed insight on InGaAs/InAlAs separate absorption, grading, charge, and multiplication avalanche photodiodes (SAGCM APDs) and a theoretical model of APDs is built. Through theoretical analysis and two-dimensional (2D) simulation, the influence of charge layer and tunneling effect on the APDs is fully understood. The design of charge layer (including doping level and thickness) can be calculated by our predictive model for different multiplication thickness. We find that as the thickness of charge layer increases, the suitable doping level range in charge layer decreases. Compared to thinner charge layer, performance of APD varies significantly via several percent deviations of doping concentrations in thicker charge layer. Moreover, the generation rate ( G btt ) of band-to-band tunnel is calculated, and the influence of tunneling effect on avalanche field was analyzed. We confirm that avalanche field and multiplication factor ( M n ) in multiplication will decrease by the tunneling effect. The theoretical model and analysis are based on InGaAs/InAlAs APD; however, they are applicable to other APD material systems as well.

A theoretical and experimental investigation of cylindrical electrostatic probes at arbitrary incidence in flowing plasma

NASA Technical Reports Server (NTRS)

Jenkins, R. V.; Jones, W. L., Jr.

1974-01-01

The theory for calculating the current collected by a negatively biased cylindrical electrostatic probe at an arbitrary angle of attack in a weakley ionized flowing plasma is presented. The theory was constructed by considering both random and directed motion simultaneous with dynamic coupling of the flow properties and of the electric field of the probe. This direct approach yielded a theory that is more general than static plasma theories modified to account for flow. Theoretical calculations are compared with experimental electrostatic probe data obtained in the free stream of an arc-heated hypersonic wind tunnel. The theoretical calculations are based on flow conditions and plasma electron densities measured by an independent microwave interferometer technique. In addition, the theory is compared with laboratory and satellite data previously published by other investigators. In each case the comparison gives good agreement.

A Review of Quality of Life after Predictive Testing for and Earlier Identification of Neurodegenerative Diseases

PubMed Central

Paulsen, Jane S.; Nance, Martha; Kim, Ji-In; Carlozzi, Noelle E.; Panegyres, Peter K.; Erwin, Cheryl; Goh, Anita; McCusker, Elizabeth; Williams, Janet K.

2013-01-01

The past decade has witnessed an explosion of evidence suggesting that many neurodegenerative diseases can be detected years, if not decades, earlier than previously thought. To date, these scientific advances have not provoked any parallel translational or clinical improvements. There is an urgency to capitalize on this momentum so earlier detection of disease can be more readily translated into improved health-related quality of life for families at risk for, or suffering with, neurodegenerative diseases. In this review, we discuss health-related quality of life (HRQOL) measurement in neurodegenerative diseases and the importance of these “patient reported outcomes” for all clinical research. Next, we address HRQOL following early identification or predictive genetic testing in some neurodegenerative diseases: Huntington disease, Alzheimer's disease, Parkinson's disease, Dementia with Lewy bodies, frontotemporal dementia, amyotrophic lateral sclerosis, prion diseases, hereditary ataxias, Dentatorubral-pallidoluysian atrophy and Wilson's disease. After a brief report of available direct-to-consumer genetic tests, we address the juxtaposition of earlier disease identification with assumed reluctance towards predictive genetic testing. Forty-one studies examining health related outcomes following predictive genetic testing for neurodegenerative disease suggested that (a) extreme or catastrophic outcomes are rare; (b) consequences commonly include transiently increased anxiety and/or depression; (c) most participants report no regret; (d) many persons report extensive benefits to receiving genetic information; and (e) stigmatization and discrimination for genetic diseases are poorly understood and policy and laws are needed. Caution is appropriate for earlier identification of neurodegenerative diseases but findings suggest further progress is safe, feasible and likely to advance clinical care. PMID:24036231

Α-aryl-N-alkyl nitrones, as potential agents for stroke treatment: synthesis, theoretical calculations, antioxidant, anti-inflammatory, neuroprotective, and brain-blood barrier permeability properties.

PubMed

Chioua, Mourad; Sucunza, David; Soriano, Elena; Hadjipavlou-Litina, Dimitra; Alcázar, Alberto; Ayuso, Irene; Oset-Gasque, María Jesús; González, María Pilar; Monjas, Leticia; Rodríguez-Franco, María Isabel; Marco-Contelles, José; Samadi, Abdelouahid

2012-01-12

We report the synthesis, theoretical calculations, the antioxidant, anti-inflammatory, and neuroprotective properties, and the ability to cross the blood-brain barrier (BBB) of (Z)-α-aryl and heteroaryl-N-alkyl nitrones as potential agents for stroke treatment. The majority of nitrones compete with DMSO for hydroxyl radicals, and most of them are potent lipoxygenase inhibitors. Cell viability-related (MTT assay) studies clearly showed that nitrones 1-3 and 10 give rise to significant neuroprotection. When compounds 1-11 were tested for necrotic cell death (LDH release test) nitrones 1-3, 6, 7, and 9 proved to be neuroprotective agents. In vitro evaluation of the BBB penetration of selected nitrones 1, 2, 10, and 11 using the PAMPA-BBB assay showed that all of them cross the BBB. Permeable quinoline nitrones 2 and 3 show potent combined antioxidant and neuroprotective properties and, therefore, can be considered as new lead compounds for further development in specific tests for potential stroke treatment.

The theoretical background to BS7167: 1990 - specification for Bordeaux connections

NASA Astrophysics Data System (ADS)

Gorley, T. A. E.

1992-03-01

The theoretical background to the specification of Bordeaux connections (components of lifting gear used to join together wire rope and a chain, or two lengths of wire rope, where the joined lengths have to run over a sheave as in the case of grabbing cranes) is documented. Decisions taken in the drafting of earlier specifications are not documented. The design criteria for BS7167:1990 are addressed. The various parts of the Bordeaux connection specified in the standard are discussed in turn: the link portion, the rope portion, and the grab shackle. Some tests on the new design undertaken by the Health and Safety Executive confirm the new design criteria to be adequate for the strengths of rope to be used with this component.

Sharper Graph-Theoretical Conditions for the Stabilization of Complex Reaction Networks

PubMed Central

Knight, Daniel; Shinar, Guy; Feinberg, Martin

2015-01-01

Across the landscape of all possible chemical reaction networks there is a surprising degree of stable behavior, despite what might be substantial complexity and nonlinearity in the governing differential equations. At the same time there are reaction networks, in particular those that arise in biology, for which richer behavior is exhibited. Thus, it is of interest to understand network-structural features whose presence enforces dull, stable behavior and whose absence permits the dynamical richness that might be necessary for life. We present conditions on a network’s Species-Reaction Graph that ensure a high degree of stable behavior, so long as the kinetic rate functions satisfy certain weak and natural constraints. These graph-theoretical conditions are considerably more incisive than those reported earlier. PMID:25600138

TheoReTS - An information system for theoretical spectra based on variational predictions from molecular potential energy and dipole moment surfaces

NASA Astrophysics Data System (ADS)

Rey, Michaël; Nikitin, Andrei V.; Babikov, Yurii L.; Tyuterev, Vladimir G.

2016-09-01

Knowledge of intensities of rovibrational transitions of various molecules and theirs isotopic species in wide spectral and temperature ranges is essential for the modeling of optical properties of planetary atmospheres, brown dwarfs and for other astrophysical applications. TheoReTS ("Theoretical Reims-Tomsk Spectral data") is an Internet accessible information system devoted to ab initio based rotationally resolved spectra predictions for some relevant molecular species. All data were generated from potential energy and dipole moment surfaces computed via high-level electronic structure calculations using variational methods for vibration-rotation energy levels and transitions. When available, empirical corrections to band centers were applied, all line intensities remaining purely ab initio. The current TheoReTS implementation contains information on four-to-six atomic molecules, including phosphine, methane, ethylene, silane, methyl-fluoride, and their isotopic species 13CH4 , 12CH3D , 12CH2D2 , 12CD4 , 13C2H4, … . Predicted hot methane line lists up to T = 2000 K are included. The information system provides the associated software for spectra simulation including absorption coefficient, absorption and emission cross-sections, transmittance and radiance. The simulations allow Lorentz, Gauss and Voight line shapes. Rectangular, triangular, Lorentzian, Gaussian, sinc and sinc squared apparatus function can be used with user-defined specifications for broadening parameters and spectral resolution. All information is organized as a relational database with the user-friendly graphical interface according to Model-View-Controller architectural tools. The full-featured web application is written on PHP using Yii framework and C++ software modules. In case of very large high-temperature line lists, a data compression is implemented for fast interactive spectra simulations of a quasi-continual absorption due to big line density. Applications for the TheoReTS may

First principles pseudopotential calculation of electron energy loss near edge structures of lattice imperfections.

PubMed

Mizoguchi, Teruyasu; Matsunaga, Katsuyuki; Tochigi, Eita; Ikuhara, Yuichi

2012-01-01

Theoretical calculations of electron energy loss near edge structures (ELNES) of lattice imperfections, particularly a Ni(111)/ZrO₂(111) heterointerface and an Al₂O₃ stacking fault on the {1100} plane, are performed using a first principles pseudopotential method. The present calculation can qualitatively reproduce spectral features as well as chemical shifts in experiment by employing a special pseudopotential designed for the excited atom with a core-hole. From the calculation, spectral changes observed in O-K ELNES from a Ni/ZrO₂ interface can be attributable to interfacial oxygen-Ni interactions. In the O-K ELNES of Al₂O₃ stacking faults, theoretical calculation suggests that the spectral feature reflects coordination environment and chemical bonding. Powerful combinations of ELNES with a pseudopotential method used to investigate the atomic and electronic structures of lattice imperfections are demonstrated. Copyright © 2011 Elsevier Ltd. All rights reserved.

Traumatic brain injury history is associated with an earlier age of dementia onset in autopsy-confirmed Alzheimer's disease.

PubMed

Schaffert, Jeff; LoBue, Christian; White, Charles L; Chiang, Hsueh-Sheng; Didehbani, Nyaz; Lacritz, Laura; Rossetti, Heidi; Dieppa, Marisara; Hart, John; Cullum, C Munro

2018-05-01

To evaluate whether a history of traumatic brain injury (TBI) with reported loss of consciousness (LOC) is a risk factor for earlier onset of Alzheimer's disease (AD) in an autopsy-confirmed sample. Data from 2,133 participants with autopsy-confirmed AD (i.e., at least Braak neurofibrillary tangle stages III to VI and CERAD neuritic plaque score moderate to frequent) were obtained from the National Alzheimer's Coordinating Center (NACC). Participants were categorized by presence/absence of self-reported remote (i.e., >1 year prior to their first Alzheimer's Disease Center visit) history of TBI with LOC (TBI+ vs. TBI-). Analyses of Covariance (ANCOVA) controlling for sex, education, and race compared groups on clinician-estimated age of symptom onset and age of diagnosis. Average age of onset was 2.34 years earlier (p = .01) for the TBI+ group (n = 194) versus the TBI- group (n = 1900). Dementia was diagnosed on average 2.83 years earlier (p = .002) in the TBI+ group (n = 197) versus the TBI- group (n = 1936). Using more stringent neuropathological criteria (i.e., Braak stages V-VI and CERAD frequent), both age of AD onset and diagnosis were 3.6 years earlier in the TBI+ group (both p's < .001). History of TBI with reported LOC appears to be a risk factor for earlier AD onset. This is the first study to use autopsy-confirmed cases, supporting previous investigations that used clinical criteria for the diagnosis of AD. Further investigation as to possible underlying mechanisms of association is needed. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

Earlier Pulmonary Valve Replacement in Down Syndrome Patients Following Tetralogy of Fallot Repair.

PubMed

Sullivan, Rachel T; Frommelt, Peter C; Hill, Garick D

2017-08-01

The association between Down syndrome and pulmonary hypertension could contribute to more severe pulmonary regurgitation after tetralogy of Fallot repair and possibly earlier pulmonary valve replacement. We compared cardiac magnetic resonance measures of pulmonary regurgitation and right ventricular dilation as well as timing of pulmonary valve replacement between those with and without Down syndrome after tetralogy of Fallot repair. Review of our surgical database from 2000 to 2015 identified patients with tetralogy of Fallot with pulmonary stenosis. Those with Down syndrome were compared to those without. The primary outcome of interest was time from repair to pulmonary valve replacement. Secondary outcomes included pulmonary regurgitation and indexed right ventricular volume on cardiac magnetic resonance imaging. The cohort of 284 patients included 35 (12%) with Down syndrome. Transannular patch repair was performed in 210 (74%). Down syndrome showed greater degree of pulmonary regurgitation (55 ± 14 vs. 37 ± 16%, p = 0.01) without a significantly greater rate of right ventricular dilation (p = 0.09). In multivariable analysis, Down syndrome (HR 2.3, 95% CI 1.2-4.5, p = 0.02) and transannular patch repair (HR 5.5, 95% CI 1.7-17.6, p = 0.004) were significant risk factors for valve replacement. Those with Down syndrome had significantly lower freedom from valve replacement (p = 0.03). Down syndrome is associated with an increased degree of pulmonary regurgitation and earlier pulmonary valve replacement after tetralogy of Fallot repair. These patients require earlier assessment by cardiac magnetic resonance imaging to determine timing of pulmonary valve replacement and evaluation for and treatment of preventable causes of pulmonary hypertension.

Earlier Parental Set Bedtimes as a Protective Factor Against Depression and Suicidal Ideation

PubMed Central

Gangwisch, James E.; Babiss, Lindsay A.; Malaspina, Dolores; Turner, J. Blake; Zammit, Gary K.; Posner, Kelly

2010-01-01

Study Objectives: To examine the relationships between parental set bedtimes, sleep duration, and depression as a quasi-experiment to explore the potentially bidirectional relationship between short sleep duration and depression. Short sleep duration has been shown to precede depression, but this could be explained as a prodromal symptom of depression. Depression in an adolescent can affect his/her chosen bedtime, but it is less likely to affect a parent's chosen set bedtime which can establish a relatively stable upper limit that can directly affect sleep duration. Design: Multivariate cross-sectional analyses of the ADD Health using logistic regression. Setting: United States nationally representative, school-based, probability-based sample in 1994-96. Participants: Adolescents (n = 15,659) in grades 7 to 12. Measurements and Results: Adolescents with parental set bedtimes of midnight or later were 24% more likely to suffer from depression (OR = 1.24, 95% CI 1.04-1.49) and 20% more likely to have suicidal ideation (1.20, 1.01-1.41) than adolescents with parental set bedtimes of 10:00 PM or earlier, after controlling for covariates. Consistent with sleep duration and perception of getting enough sleep acting as mediators, the inclusion of these variables in the multivariate models appreciably attenuated the associations for depression (1.07, 0.88-1.30) and suicidal ideation (1.09, 0.92-1.29). Conclusions: The results from this study provide new evidence to strengthen the argument that short sleep duration could play a role in the etiology of depression. Earlier parental set bedtimes could therefore be protective against adolescent depression and suicidal ideation by lengthening sleep duration. Citation: Gangwisch JE; Babiss LA; Malaspina D; Turner JB; Zammit GK; Posner K. Earlier parental set bedtimes as a protective factor against depression and suicidal ideation. SLEEP 2010;33(1):97-106. PMID:20120626

40 CFR 87.21 - Exhaust emission standards for Tier 4 and earlier engines.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Emissions (New Aircraft Gas Turbine Engines) § 87.21 Exhaust emission standards for Tier 4 and earlier... standards. (a) Exhaust emissions of smoke from each new aircraft gas turbine engine of class T8 manufactured... from each new aircraft gas turbine engine of class TF and of rated output of 129 kilonewtons thrust or...

40 CFR 87.21 - Exhaust emission standards for Tier 4 and earlier engines.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Emissions (New Aircraft Gas Turbine Engines) § 87.21 Exhaust emission standards for Tier 4 and earlier... standards. (a) Exhaust emissions of smoke from each new aircraft gas turbine engine of class T8 manufactured... from each new aircraft gas turbine engine of class TF and of rated output of 129 kilonewtons thrust or...

Calculation of Transverse-Momentum-Dependent Evolution for Sivers Transverse Single Spin Asymmetry Measurements

NASA Astrophysics Data System (ADS)

Aybat, S. Mert; Prokudin, Alexei; Rogers, Ted C.

2012-06-01

The Sivers transverse single spin asymmetry (TSSA) is calculated and compared at different scales using the transverse-momentum-dependent (TMD) evolution equations applied to previously existing extractions. We apply the Collins-Soper-Sterman (CSS) formalism, using the version recently developed by Collins. Our calculations rely on the universality properties of TMD functions that follow from the TMD-factorization theorem. Accordingly, the nonperturbative input is fixed by earlier experimental measurements, including both polarized semi-inclusive deep inelastic scattering (SIDIS) and unpolarized Drell-Yan (DY) scattering. It is shown that recent preliminary COMPASS measurements are consistent with the suppression prescribed by TMD evolution.

Theoretical investigation on the magnetic and electric properties in TbSb compound through an anisotropic microscopic model

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

Ranke, P. J. von, E-mail: von.ranke@uol.com.br; Ribeiro, P. O.; Alho, B. P.

2016-05-14

We report the strong correlations between the magnetoresistivity and the magnetic entropy change in the cubic antiferromagnetic TbSb compound. The theoretical investigation was performed through a microscopic model which takes into account the crystalline electrical field anisotropy, exchange coupling interactions between the up and down magnetic sublattices, and the Zeeman interaction. The easy magnetization directions changes from 〈001〉 to 〈110〉 and then to 〈111〉 observed experimentally was successfully theoretically described. Also, the calculation of the temperature dependence of electric resistivity showed good agreement with the experimental data. Theoretical predictions were calculated for the temperature dependence of the magnetic entropy andmore » resistivity changes upon magnetic field variation. Besides, the difference in the spin up and down sublattices resistivity was investigated.« less

Reducing Older Driver Motor Vehicle Collisions via Earlier Cataract Surgery

PubMed Central

Mennemeyer, Stephen T.; Owsley, Cynthia; McGwin, Gerald

2013-01-01

Older adults who undergo cataract extraction have roughly half the rate of motor vehicle collision (MVC) involvement per mile driven compared to cataract patients who do not elect cataract surgery. Currently in the U.S., most insurers do not allow payment for cataract surgery based upon the findings of a vision exam unless accompanied by an individual’s complaint of visual difficulties that seriously interfere with driving or other daily activities and individuals themselves may be slow or reluctant to complain and seek relief. As a consequence, surgery tends to occur after significant vision problems have emerged. We hypothesize that a proactive policy encouraging cataract surgery earlier for a lesser level of complaint would significantly reduce MVCs among older drivers. We used a Monte Carlo model to simulate the MVC experience of the U.S. population from age 60 to 89 under alternative protocols for the timing of cataract surgery which we call “Current Practice” (CP) and “Earlier Surgery” (ES). Our base model finds, from a societal perspective with undiscounted 2010 dollars, that switching to ES from CP reduces by about 21% the average number of MVCs, fatalities, and MVC cost per person. The net effect on total cost – all MVC costs plus cataract surgery expenditures -- is a reduction of about 16%. Quality Adjusted Life Years would increase by about 5%. From the perspective of payers for healthcare, the switch would increase cataract surgery expenditure for ages 65+ by about 8% and for ages 60 to 64 by about 47% but these expenditures are substantially offset after age 65 by reductions in the medical and emergency services component of MVC cost. Similar results occur with discounting at 3% and with various sensitivity analyses. We conclude that a policy of ES would significantly reduce MVCs and their associated consequences. PMID:23369786

The guanidine and maleic acid (1:1) complex. The additional theoretical and experimental studies.

PubMed

Drozd, Marek; Dudzic, Damian

2012-04-01

On the basis of experimental literature data the theoretical studies for guanidinium and maleic acid complex with using DFT method are performed. In these studies the experimental X-ray data for two different forms of investigated crystal were used. During the geometry optimization process one equilibrium structure was found, only. According to this result the infrared spectrum for one theoretical molecule was calculated. On the basis of potential energy distribution (PED) analysis the clear-cut assignments of observed bands were performed. For the calculated molecule with energy minimum the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were obtained and graphically illustrated. The energy difference (GAP) between HOMO and LUMO was analyzed. Additionally, the nonlinear properties of this molecule were calculated. The α and β (first and second order) hyperpolarizability values are obtained. On the basis of these results the title crystal was classified as new second order NLO generator. Copyright © 2011 Elsevier B.V. All rights reserved.

Application of proteotyping Strain Solution™ ver. 2 software and theoretically calculated mass database in MALDI-TOF MS typing of Salmonella serotype.

PubMed

Ojima-Kato, Teruyo; Yamamoto, Naomi; Nagai, Satomi; Shima, Keisuke; Akiyama, Yumi; Ota, Junji; Tamura, Hiroto

2017-12-01

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS)-based microbial identification is a popular analytical method. Strain Solution proteotyping software available for MALDI-TOF MS has great potential for the precise and detailed discrimination of microorganisms at serotype- or strain-level, beyond the conventional mass fingerprinting approaches. Here, we constructed a theoretically calculated mass database of Salmonella enterica subspecies enterica consisting of 12 biomarker proteins: ribosomal proteins S8, L15, L17, L21, L25, and S7, Mn-cofactor-containing superoxide dismutase (SodA), peptidyl-prolyl cis-trans isomerase C (PPIase C), and protein Gns, and uncharacterized proteins YibT, YaiA, and YciF, that can allow serotyping of Salmonella. Strain Solution ver. 2 software with the novel database constructed in this study demonstrated that 109 strains (94%), including the major outbreak-associated serotypes, Enteritidis, Typhimurium, and Infantis, could be correctly identified from others by colony-directed MALDI-TOF MS using 116 strains belonging to 23 kinds of typed and untyped serotypes of S. enterica from culture collections, patients, and foods. We conclude that Strain Solution ver. 2 software integrated with the accurate mass database will be useful for the bacterial proteotyping by MALDI-TOF MS-based microbial classification in the clinical and food safety fields.

Convergence of highly parallel stray field calculation using the fast multipole method on irregular meshes

NASA Astrophysics Data System (ADS)

Palmesi, P.; Abert, C.; Bruckner, F.; Suess, D.

2018-05-01

Fast stray field calculation is commonly considered of great importance for micromagnetic simulations, since it is the most time consuming part of the simulation. The Fast Multipole Method (FMM) has displayed linear O(N) parallelization behavior on many cores. This article investigates the error of a recent FMM approach approximating sources using linear—instead of constant—finite elements in the singular integral for calculating the stray field and the corresponding potential. After measuring performance in an earlier manuscript, this manuscript investigates the convergence of the relative L2 error for several FMM simulation parameters. Various scenarios either calculating the stray field directly or via potential are discussed.

Simple theoretical determination of the thickness of an alkali monolayer adsorbed on a jellium surface

NASA Astrophysics Data System (ADS)

Wojciechowski, K. F.; Rogowska, J. M.; Bogdanów, H.

1991-05-01

The thickness of a jellium slab representing an alkali monolayer on a jellium surface has been calculated, using parametrized trial functions for the electron density profile at the surface fulfilling the Budd-Vannimenus theorem and the charge neutrality condition. Reasonable values of the thicknesses of potassium, sodium, rubidium and caesium monolayers are obtained, which, contrary to earlier assumptions, depend on the bulk electron density of the substrate.

Theoretical electron-impact-ionization cross section for Fe11+ forming Fe12+

NASA Astrophysics Data System (ADS)

Kwon, Duck-Hee; Savin, Daniel Wolf

2012-08-01

We have calculated cross sections for electron impact ionization (EII) of P-like Fe11+ forming Si-like Fe12+. We have used the flexible atomic code (FAC) and a distorted-wave (DW) approximation. Particular attention has been paid to the ionization through the 3l→nl' and 2l→nl' excitation autoionization (EA) channels. We compare our results to previously published FAC DW results and recent experimental results. We find that the previous discrepancy between theory and experiment at the EII threshold can be accounted for by the 3l→nl' EA channels which were not included in the earlier calculations. At higher energies the discrepancy previously seen between theory and experiment for the magnitude of the 2l→nl'(n≥4) EA remains, though the difference has been reduced by our newer results. The resulting Maxwellian rate coefficient derived from our calculations lies within 11% of the experimentally derived rate coefficient in the temperature range where Fe11+ forms in collisional ionization equilibrium.

Daily Use, Especially of High-Potency Cannabis, Drives the Earlier Onset of Psychosis in Cannabis Users

PubMed Central

Di Forti, Marta; Sallis, Hannah; Allegri, Fabio; Trotta, Antonella; Ferraro, Laura; Stilo, Simona A.; Marconi, Arianna; La Cascia, Caterina; Reis Marques, Tiago; Pariante, Carmine; Dazzan, Paola; Mondelli, Valeria; Paparelli, Alessandra; Kolliakou, Anna; Prata, Diana; Gaughran, Fiona; David, Anthony S.; Morgan, Craig; Stahl, Daniel; Khondoker, Mizanur; MacCabe, James H.; Murray, Robin M.

2014-01-01

Cannabis use is associated with an earlier age of onset of psychosis (AOP). However, the reasons for this remain debated. Methods: We applied a Cox proportional hazards model to 410 first-episode psychosis patients to investigate the association between gender, patterns of cannabis use, and AOP. Results: Patients with a history of cannabis use presented with their first episode of psychosis at a younger age (mean years = 28.2, SD = 8.0; median years = 27.1) than those who never used cannabis (mean years = 31.4, SD = 9.9; median years = 30.0; hazard ratio [HR] = 1.42; 95% CI: 1.16–1.74; P < .001). This association remained significant after controlling for gender (HR = 1.39; 95% CI: 1.11–1.68; P < .001). Those who had started cannabis at age 15 or younger had an earlier onset of psychosis (mean years = 27.0, SD = 6.2; median years = 26.9) than those who had started after 15 years (mean years = 29.1, SD = 8.5; median years = 27.8; HR = 1.40; 95% CI: 1.06–1.84; P = .050). Importantly, subjects who had been using high-potency cannabis (skunk-type) every day had the earliest onset (mean years = 25.2, SD = 6.3; median years = 24.6) compared to never users among all the groups tested (HR = 1.99; 95% CI: 1.50- 2.65; P < .0001); these daily users of high-potency cannabis had an onset an average of 6 years earlier than that of non-cannabis users. Conclusions: Daily use, especially of high-potency cannabis, drives the earlier onset of psychosis in cannabis users. PMID:24345517

Calculating the dim light melatonin onset: the impact of threshold and sampling rate.

PubMed

Molina, Thomas A; Burgess, Helen J

2011-10-01

The dim light melatonin onset (DLMO) is the most reliable circadian phase marker in humans, but the cost of assaying samples is relatively high. Therefore, the authors examined differences between DLMOs calculated from hourly versus half-hourly sampling and differences between DLMOs calculated with two recommended thresholds (a fixed threshold of 3 pg/mL and a variable "3k" threshold equal to the mean plus two standard deviations of the first three low daytime points). The authors calculated these DLMOs from salivary dim light melatonin profiles collected from 122 individuals (64 women) at baseline. DLMOs derived from hourly sampling occurred on average only 6-8 min earlier than the DLMOs derived from half-hourly saliva sampling, and they were highly correlated with each other (r ≥ 0.89, p < .001). However, in up to 19% of cases the DLMO derived from hourly sampling was >30 min from the DLMO derived from half-hourly sampling. The 3 pg/mL threshold produced significantly less variable DLMOs than the 3k threshold. However, the 3k threshold was significantly lower than the 3 pg/mL threshold (p < .001). The DLMOs calculated with the 3k method were significantly earlier (by 22-24 min) than the DLMOs calculated with the 3 pg/mL threshold, regardless of sampling rate. These results suggest that in large research studies and clinical settings, the more affordable and practical option of hourly sampling is adequate for a reasonable estimate of circadian phase. Although the 3 pg/mL fixed threshold is less variable than the 3k threshold, it produces estimates of the DLMO that are further from the initial rise of melatonin.

Evaluating the Theoretic Adequacy and Applied Potential of Computational Models of the Spacing Effect.

PubMed

Walsh, Matthew M; Gluck, Kevin A; Gunzelmann, Glenn; Jastrzembski, Tiffany; Krusmark, Michael

2018-06-01

The spacing effect is among the most widely replicated empirical phenomena in the learning sciences, and its relevance to education and training is readily apparent. Yet successful applications of spacing effect research to education and training is rare. Computational modeling can provide the crucial link between a century of accumulated experimental data on the spacing effect and the emerging interest in using that research to enable adaptive instruction. In this paper, we review relevant literature and identify 10 criteria for rigorously evaluating computational models of the spacing effect. Five relate to evaluating the theoretic adequacy of a model, and five relate to evaluating its application potential. We use these criteria to evaluate a novel computational model of the spacing effect called the Predictive Performance Equation (PPE). Predictive Performance Equation combines elements of earlier models of learning and memory including the General Performance Equation, Adaptive Control of Thought-Rational, and the New Theory of Disuse, giving rise to a novel computational account of the spacing effect that performs favorably across the complete sets of theoretic and applied criteria. We implemented two other previously published computational models of the spacing effect and compare them to PPE using the theoretic and applied criteria as guides. Copyright © 2018 Cognitive Science Society, Inc.

Spectral and structural studies of the anti-cancer drug Flutamide by density functional theoretical method

NASA Astrophysics Data System (ADS)

Mariappan, G.; Sundaraganesan, N.

2014-01-01

A comprehensive screening of the more recent DFT theoretical approach to structural analysis is presented in this section of theoretical structural analysis. The chemical name of 2-methyl-N-[4-nitro-3-(trifluoromethyl)phenyl]-propanamide is usually called as Flutamide (In the present study it is abbreviated as FLT) and is an important and efficacious drug in the treatment of anti-cancer resistant. The molecular geometry, vibrational spectra, electronic and NMR spectral interpretation of Flutamide have been studied with the aid of density functional theory method (DFT). The vibrational assignments of the normal modes were performed on the basis of the PED calculations using the VEDA 4 program. Comparison of computational results with X-ray diffraction results of Flutamide allowed the evaluation of structure predictions and confirmed B3LYP/6-31G(d,p) as accurate for structure determination. Application of scaling factors for IR and Raman frequency predictions showed good agreement with experimental values. This is supported the assignment of the major contributors of the vibration modes of the title compound. Stability of the molecule arising from hyperconjugative interactions leading to its bioactivity, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. NMR chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. The comparison of measured FTIR, FT-Raman, and UV-Visible data to calculated values allowed assignment of major spectral features of the title molecule. Besides, Frontier molecular orbital analyze was also investigated using theoretical calculations.

Experimental and theoretical study on THz spectrum artesunate

NASA Astrophysics Data System (ADS)

Zhang, Ai-Bing; Kong, Ling-Gao; Wang, Shi-Jin; Li, Lei; Zheng, Xiang-Zhi

2008-10-01

Artesunate is a very effective drug to treat malaria. They are studied experimentally by Terahertz (THz) time-domain spectroscopy (THz-TDS), and the characteristic absorption spectra are obtained in the range of 0.2 to 2.6 THz. The vibrational frequencies are calculated using the density functional theory (DFT). Theoretical results show that 0.71, 1.94 and 2.46 THz are significant agreement with the experimental results in 0.87, 1.82 and 2.46THz, and identification of vibrational modes are given. The calculated results further confirm that the characteristic frequencies come from the collective vibrational modes. The results suggest that the use of the THz-TDS technique can be an effective way to inspect for Chinese medicine.

Calculating the Responses of Self-Powered Radiation Detectors.

NASA Astrophysics Data System (ADS)

Thornton, D. A.

Available from UMI in association with The British Library. The aim of this research is to review and develop the theoretical understanding of the responses of Self -Powered Radiation Detectors (SPDs) in Pressurized Water Reactors (PWRs). Two very different models are considered. A simple analytic model of the responses of SPDs to neutrons and gamma radiation is presented. It is a development of the work of several previous authors and has been incorporated into a computer program (called GENSPD), the predictions of which have been compared with experimental and theoretical results reported in the literature. Generally, the comparisons show reasonable consistency; where there is poor agreement explanations have been sought and presented. Two major limitations of analytic models have been identified; neglect of current generation in insulators and over-simplified electron transport treatments. Both of these are developed in the current work. A second model based on the Explicit Representation of Radiation Sources and Transport (ERRST) is presented and evaluated for several SPDs in a PWR at beginning of life. The model incorporates simulation of the production and subsequent transport of neutrons, gamma rays and electrons, both internal and external to the detector. Neutron fluxes and fuel power ratings have been evaluated with core physics calculations. Neutron interaction rates in assembly and detector materials have been evaluated in lattice calculations employing deterministic transport and diffusion methods. The transport of the reactor gamma radiation has been calculated with Monte Carlo, adjusted diffusion and point-kernel methods. The electron flux associated with the reactor gamma field as well as the internal charge deposition effects of the transport of photons and electrons have been calculated with coupled Monte Carlo calculations of photon and electron transport. The predicted response of a SPD is evaluated as the sum of contributions from individual

Calculation of long range forces and their applications in determining gaseous properties

NASA Technical Reports Server (NTRS)

Singh, J. J.

1979-01-01

A discussion of various theoretical and experimental techniques for the calculation of long range interaction between two atomic systems at moderate separation is presented. Some applications of these techniques for obtaining gaseous properties are described. The forces between neutral molecules and metallic surfaces are also discussed and numerical values of heats of adsorption for a number of systems are calculated.

Atomic Calculations and Laboratory Measurements Relevant to X-ray Warm Absorbers

NASA Technical Reports Server (NTRS)

Kallman, Tim; Bautista, M.; Palmeri, P.

2007-01-01

This viewgraph document reviews the atomic calculations and the measurements from the laboratory that are relevant to our understanding of X-Ray Warm Absorbers. Included is a brief discussion of the theoretical and the experimental tools. Also included is a discussion of the challenges, and calculations relevant to dielectronic recombination, photoionization cross sections, and collisional ionization. A review of the models is included, and the sequence that the models were applied.

A /sup 1/Pi--X /sup 1/. sigma. /sup +/ band system in CH/sup +/ and CD/sup +/: theoretical spectroscopic constants and lifetimes

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

Elander, N.; Oddershede, J.; Beebe, N.H.F.

1977-08-15

Polarization propagator calculation of spectroscopic constants and radiative lifetimes for the A /sup 1/Pi--X /sup 1/..sigma../sup +/ band system are presented. The spectroscopic constants agree well with experimental and other theoretical values. We have also performed an iterative Rydberg-Klein-Rees (RKR) calculation of B/sub e/, ..omega../sub e/, and ..omega../sub e/x/sub e/ for the experimental X /sup 1/..sigma../sup +/ state.The calculated radiative lifetime for the A /sup 1/Pi state (v'=0) is 660 ns and 598 ns, with theoretical and experimental potential energy curves, respectively. This difference (about 60 ns) indicates the inaccuracy in the present calculation. Experimentally the most recent estimate ofmore » the A /sup 1/Pi (v'=0) state is 630 +- 50 ns, and theoretically the Yoshimine et al. transition moment gives tau (A /sup 1/Pi, v'=0) =722 ns.The radiative lifetimes calculated for CD/sup +/ are between 1.3% and 3.9% larger than the corresponding CH/sup +/ lifetimes.« less

Charge and Spin States in Schiff Base Metal Complexes with a Disiloxane Unit Exhibiting a Strong Noninnocent Ligand Character: Synthesis, Structure, Spectroelectrochemistry, and Theoretical Calculations.

PubMed

Cazacu, Maria; Shova, Sergiu; Soroceanu, Alina; Machata, Peter; Bucinsky, Lukas; Breza, Martin; Rapta, Peter; Telser, Joshua; Krzystek, J; Arion, Vladimir B

2015-06-15

Mononuclear nickel(II), copper(II), and manganese(III) complexes with a noninnocent tetradentate Schiff base ligand containing a disiloxane unit were prepared in situ by reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with 1,3-bis(3-aminopropyl)tetramethyldisiloxane followed by addition of the appropriate metal(II) salt. The ligand H2L resulting from these reactions is a 2:1 condensation product of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with 1,3-bis(3-aminopropyl)tetramethyldisiloxane. The resulting metal complexes, NiL·0.5CH2Cl2, CuL·1.5H2O, and MnL(OAc)·0.15H2O, were characterized by elemental analysis, spectroscopic methods (IR, UV-vis, X-band EPR, HFEPR, (1)H NMR), ESI mass spectrometry, and single crystal X-ray diffraction. Taking into account the well-known strong stabilizing effects of tert-butyl groups in positions 3 and 5 of the aromatic ring on phenoxyl radicals, we studied the one-electron and two-electron oxidation of the compounds using both experimental (chiefly spectroelectrochemistry) and computational (DFT) techniques. The calculated spin-density distribution and localized orbitals analysis revealed the oxidation locus and the effect of the electrochemical electron transfer on the molecular structure of the complexes, while time-dependent DFT calculations helped to explain the absorption spectra of the electrochemically generated species. Hyperfine coupling constants, g-tensors, and zero-field splitting parameters have been calculated at the DFT level of theory. Finally, the CASSCF approach has been employed to theoretically explore the zero-field splitting of the S = 2 MnL(OAc) complex for comparison purposes with the DFT and experimental HFEPR results. It is found that the D parameter sign strongly depends on the metal coordination geometry.

Automated Transition State Theory Calculations for High-Throughput Kinetics.

PubMed

Bhoorasingh, Pierre L; Slakman, Belinda L; Seyedzadeh Khanshan, Fariba; Cain, Jason Y; West, Richard H

2017-09-21

A scarcity of known chemical kinetic parameters leads to the use of many reaction rate estimates, which are not always sufficiently accurate, in the construction of detailed kinetic models. To reduce the reliance on these estimates and improve the accuracy of predictive kinetic models, we have developed a high-throughput, fully automated, reaction rate calculation method, AutoTST. The algorithm integrates automated saddle-point geometry search methods and a canonical transition state theory kinetics calculator. The automatically calculated reaction rates compare favorably to existing estimated rates. Comparison against high level theoretical calculations show the new automated method performs better than rate estimates when the estimate is made by a poor analogy. The method will improve by accounting for internal rotor contributions and by improving methods to determine molecular symmetry.

Long-term effects of earlier initiated continuous Kangaroo Mother Care (KMC) for low-birth-weight (LBW) infants in Madagascar.

PubMed

Nagai, Shuko; Yonemoto, Naohiro; Rabesandratana, Norotiana; Andrianarimanana, Diavolana; Nakayama, Takeo; Mori, Rintaro

2011-12-01

To examine the long-term effects of earlier initiated continuous Kangaroo Mother Care (KMC) for relatively stable low-birth-weight (LBW) infants in a resource-limited country. A randomized controlled trial with long-term follow-up was performed in LBW infants in Madagascar. Earlier continuous KMC (intervention group) was initiated as soon as possible within 24 h postbirth, and later continuous KMC (control group: conventional care) was initiated after complete stabilization. Outcome measures were mortality or readmission, nutritional indicators at 6-12 months postbirth and feeding condition at 6 months postbirth (ClinicalTrials.gov, NCT00531492). A total of 72 infants were followed for mortality or readmission at 6-12 months postbirth. There was no difference between the two groups (7/36 vs. 7/36, Risk ratio (RR), 1.00; 95% CIs, 0.39-2.56; p = 1.00). The proportion of exclusive breast feeding (EBF) at 6 months postbirth was significantly higher with earlier KMC than later KMC (12/29 vs. 4/26; RR 2.69; 95% CIs, 1.00-7.31; p = 0.04). There were no differences in nutritional indicators between the two groups at 6-12 months postbirth. Earlier initiated continuous KMC results in a significantly higher proportion of EBF at 6 months postbirth. Further larger-scale long-term evaluations of earlier initiated continuous KMC for LBW infants are needed. © 2011 The Author(s)/Acta Paediatrica © 2011 Foundation Acta Paediatrica.

Facilitating earlier transfer of care from acute stroke services into the community.

PubMed

Robinson, Jennifer

This article outlines an initiative to reduce length of stay for stroke patients within an acute hospital and to facilitate earlier transfer of care. Existing care provision was remodelled and expanded to deliver stroke care to patients within a community bed-based intermediate care facility or intermediate care at home. This new model of care has improved the delivery of rehabilitation through alternative and innovative ways of addressing service delivery that meet the needs of the patients.

A vantage from space can detect earlier drought onset: an approach using relative humidity.

PubMed

Farahmand, Alireza; AghaKouchak, Amir; Teixeira, Joao

2015-02-25

Each year, droughts cause significant economic and agricultural losses across the world. The early warning and onset detection of drought is of particular importance for effective agriculture and water resource management. Previous studies show that the Standard Precipitation Index (SPI), a measure of precipitation deficit, detects drought onset earlier than other indicators. Here we show that satellite-based near surface air relative humidity data can further improve drought onset detection and early warning. This paper introduces the Standardized Relative Humidity Index (SRHI) based on the NASA Atmospheric Infrared Sounder (AIRS) observations. The results indicate that the SRHI typically detects the drought onset earlier than the SPI. While the AIRS mission was not originally designed for drought monitoring, we show that its relative humidity data offers a new and unique avenue for drought monitoring and early warning. We conclude that the early warning aspects of SRHI may have merit for integration into current drought monitoring systems.

A Vantage from Space Can Detect Earlier Drought Onset: An Approach Using Relative Humidity

PubMed Central

Farahmand, Alireza; AghaKouchak, Amir; Teixeira, Joao

2015-01-01

Each year, droughts cause significant economic and agricultural losses across the world. The early warning and onset detection of drought is of particular importance for effective agriculture and water resource management. Previous studies show that the Standard Precipitation Index (SPI), a measure of precipitation deficit, detects drought onset earlier than other indicators. Here we show that satellite-based near surface air relative humidity data can further improve drought onset detection and early warning. This paper introduces the Standardized Relative Humidity Index (SRHI) based on the NASA Atmospheric Infrared Sounder (AIRS) observations. The results indicate that the SRHI typically detects the drought onset earlier than the SPI. While the AIRS mission was not originally designed for drought monitoring, we show that its relative humidity data offers a new and unique avenue for drought monitoring and early warning. We conclude that the early warning aspects of SRHI may have merit for integration into current drought monitoring systems. PMID:25711500

Computer program for assessing the theoretical performance of a three dimensional inlet

NASA Technical Reports Server (NTRS)

Agnone, A. M.; Kung, F.

1972-01-01

A computer program for determining the theoretical performance of a three dimensional inlet is presented. An analysis for determining the capture area, ram force, spillage force, and surface pressure force is presented, along with the necessary computer program. A sample calculation is also included.

Detection, attribution, and sensitivity of trends toward earlier streamflow in the Sierra Nevada

USGS Publications Warehouse

Maurer, E.P.; Stewart, I.T.; Bonfils, Celine; Duffy, P.B.; Cayan, D.

2007-01-01

Observed changes in the timing of snowmelt dominated streamflow in the western United States are often linked to anthropogenic or other external causes. We assess whether observed streamflow timing changes can be statistically attributed to external forcing, or whether they still lie within the bounds of natural (internal) variability for four large Sierra Nevada (CA) basins, at inflow points to major reservoirs. Streamflow timing is measured by "center timing" (CT), the day when half the annual flow has passed a given point. We use a physically based hydrology model driven by meteorological input from a global climate model to quantify the natural variability in CT trends. Estimated 50-year trends in CT due to natural climate variability often exceed estimated actual CT trends from 1950 to 1999. Thus, although observed trends in CT to date may be statistically significant, they cannot yet be statistically attributed to external influences on climate. We estimate that projected CT changes at the four major reservoir inflows will, with 90% confidence, exceed those from natural variability within 1-4 decades or 4-8 decades, depending on rates of future greenhouse gas emissions. To identify areas most likely to exhibit CT changes in response to rising temperatures, we calculate changes in CT under temperature increases from 1 to 5??. We find that areas with average winter temperatures between -2??C and -4??C are most likely to respond with significant CT shifts. Correspondingly, elevations from 2000 to 2800 in are most sensitive to temperature increases, with CT changes exceeding 45 days (earlier) relative to 1961-1990. Copyright 2007 by the American Geophysical Union.

Experimental and theoretical studies of near-ground acoustic radiation propagation in the atmosphere

NASA Astrophysics Data System (ADS)

Belov, Vladimir V.; Burkatovskaya, Yuliya B.; Krasnenko, Nikolai P.; Rakov, Aleksandr S.; Rakov, Denis S.; Shamanaeva, Liudmila G.

2017-11-01

Results of experimental and theoretical studies of the process of near-ground propagation of monochromatic acoustic radiation on atmospheric paths from a source to a receiver taking into account the contribution of multiple scattering on fluctuations of atmospheric temperature and wind velocity, refraction of sound on the wind velocity and temperature gradients, and its reflection by the underlying surface for different models of the atmosphere depending the sound frequency, coefficient of reflection from the underlying surface, propagation distance, and source and receiver altitudes are presented. Calculations were performed by the Monte Carlo method using the local estimation algorithm by the computer program developed by the authors. Results of experimental investigations under controllable conditions are compared with theoretical estimates and results of analytical calculations for the Delany-Bazley impedance model. Satisfactory agreement of the data obtained confirms the correctness of the suggested computer program.

Experimental and theoretical IR and Raman spectra of picolinic, nicotinic and isonicotinic acids

NASA Astrophysics Data System (ADS)

Koczoń, P.; Dobrowolski, J. Cz.; Lewandowski, W.; Mazurek, A. P.

2003-07-01

The experimental and theoretical (B3PW91/6-311++G**) vibrational (IR and Raman) spectra of picolinic, nicotinic and isonicotinic acids (pyridine-2-, -3-, and -4-carboxylic acid, respectively) were studied. Three stable calculated structures were found for picolinic acid: the structure with intramolecular hydrogen COOH⋯N bond, and the two without hydrogen bond. For the nicotinic acid two stable theoretical structures differ in orientation of the COOH group with respect to the nitrogen atom, whereas for the isonicotinic acid only one form was stable. The theoretical vibrational spectra of the three acids were interpreted by means of potential energy distributions (PEDs) using VEDA 3 program. Next, selected experimental bands were assigned based on the scaled theoretical wavenumbers. Finally, the wavenumbers and intensities for the three isomeric acids were compared and discussed in terms of location of the carboxylic group.

Praxis and reflexivity for interprofessional education: towards an inclusive theoretical framework for learning.

PubMed

Hutchings, Maggie; Scammell, Janet; Quinney, Anne

2013-09-01

While there is growing evidence of theoretical perspectives adopted in interprofessional education, learning theories tend to foreground the individual, focusing on psycho-social aspects of individual differences and professional identity to the detriment of considering social-structural factors at work in social practices. Conversely socially situated practice is criticised for being context-specific, making it difficult to draw generalisable conclusions for improving interprofessional education. This article builds on a theoretical framework derived from earlier research, drawing on the dynamics of Dewey's experiential learning theory and Archer's critical realist social theory, to make a case for a meta-theoretical framework enabling social-constructivist and situated learning theories to be interlinked and integrated through praxis and reflexivity. Our current analysis is grounded in an interprofessional curriculum initiative mediated by a virtual community peopled by health and social care users. Student perceptions, captured through quantitative and qualitative data, suggest three major disruptive themes, creating opportunities for congruence and disjuncture and generating a model of zones of interlinked praxis associated with professional differences and identity, pedagogic strategies and technology-mediated approaches. This model contributes to a framework for understanding the complexity of interprofessional learning and offers bridges between individual and structural factors for engaging with the enablements and constraints at work in communities of practice and networks for interprofessional education.

Vibrational spectroscopic studies and DFT calculations of 4-aminoantipyrine

NASA Astrophysics Data System (ADS)

Swaminathan, J.; Ramalingam, M.; Sethuraman, V.; Sundaraganesan, N.; Sebastian, S.

2009-08-01

The pyrazole derivative, 4-aminoantipyrine (4AAP), used as an intermediate for the synthesis of pharmaceuticals especially antipyretic and analgesic drugs has been analyzed experimentally and theoretically for its vibrational frequencies. The FTIR and FT Raman spectra of the title compound have been compared with the theoretically computed frequencies invoking the standard 6-311g(d,p) and cc-pVDZ basis sets at DFT level of theory (B3LYP). The harmonic vibrational frequencies at B3LYP/cc-pVDZ after appropriate scaling method seem to coincide satisfactorily with the experimental observations rather than B3LYP/6-311g(d,p) results. The theoretical spectrograms for FT-IR and FT-Raman spectra of 4AAP have been also constructed and compared with the experimental spectra. Additionally, thermodynamic data have also been calculated and discussed.

Daily use, especially of high-potency cannabis, drives the earlier onset of psychosis in cannabis users.

PubMed

Di Forti, Marta; Sallis, Hannah; Allegri, Fabio; Trotta, Antonella; Ferraro, Laura; Stilo, Simona A; Marconi, Arianna; La Cascia, Caterina; Reis Marques, Tiago; Pariante, Carmine; Dazzan, Paola; Mondelli, Valeria; Paparelli, Alessandra; Kolliakou, Anna; Prata, Diana; Gaughran, Fiona; David, Anthony S; Morgan, Craig; Stahl, Daniel; Khondoker, Mizanur; MacCabe, James H; Murray, Robin M

2014-11-01

Cannabis use is associated with an earlier age of onset of psychosis (AOP). However, the reasons for this remain debated. We applied a Cox proportional hazards model to 410 first-episode psychosis patients to investigate the association between gender, patterns of cannabis use, and AOP. Patients with a history of cannabis use presented with their first episode of psychosis at a younger age (mean years = 28.2, SD = 8.0; median years = 27.1) than those who never used cannabis (mean years = 31.4, SD = 9.9; median years = 30.0; hazard ratio [HR] = 1.42; 95% CI: 1.16-1.74; P < .001). This association remained significant after controlling for gender (HR = 1.39; 95% CI: 1.11-1.68; P < .001). Those who had started cannabis at age 15 or younger had an earlier onset of psychosis (mean years = 27.0, SD = 6.2; median years = 26.9) than those who had started after 15 years (mean years = 29.1, SD = 8.5; median years = 27.8; HR = 1.40; 95% CI: 1.06-1.84; P = .050). Importantly, subjects who had been using high-potency cannabis (skunk-type) every day had the earliest onset (mean years = 25.2, SD = 6.3; median years = 24.6) compared to never users among all the groups tested (HR = 1.99; 95% CI: 1.50- 2.65; P < .0001); these daily users of high-potency cannabis had an onset an average of 6 years earlier than that of non-cannabis users. Daily use, especially of high-potency cannabis, drives the earlier onset of psychosis in cannabis users. © The Author 2013. Published by Oxford University Press on behalf of the Maryland Psychiatric Research Center. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Good practices in free-energy calculations.

PubMed

Pohorille, Andrew; Jarzynski, Christopher; Chipot, Christophe

2010-08-19

As access to computational resources continues to increase, free-energy calculations have emerged as a powerful tool that can play a predictive role in a wide range of research areas. Yet, the reliability of these calculations can often be improved significantly if a number of precepts, or good practices, are followed. Although the theory upon which these good practices rely has largely been known for many years, it is often overlooked or simply ignored. In other cases, the theoretical developments are too recent for their potential to be fully grasped and merged into popular platforms for the computation of free-energy differences. In this contribution, the current best practices for carrying out free-energy calculations using free energy perturbation and nonequilibrium work methods are discussed, demonstrating that at little to no additional cost, free-energy estimates could be markedly improved and bounded by meaningful error estimates. Monitoring the probability distributions that underlie the transformation between the states of interest, performing the calculation bidirectionally, stratifying the reaction pathway, and choosing the most appropriate paradigms and algorithms for transforming between states offer significant gains in both accuracy and precision.

Recent Theoretical Studies On Excitation and Recombination

NASA Technical Reports Server (NTRS)

Pradhan, Anil K.

2000-01-01

New advances in the theoretical treatment of atomic processes in plasmas are described. These enable not only an integrated, unified, and self-consistent treatment of important radiative and collisional processes, but also large-scale computation of atomic data with high accuracy. An extension of the R-matrix work, from excitation and photoionization to electron-ion recombination, includes a unified method that subsumes both the radiative and the di-electronic recombination processes in an ab initio manner. The extensive collisional calculations for iron and iron-peak elements under the Iron Project are also discussed.

Theoretical analysis of a ceramic plate thickness-shear mode piezoelectric transformer.

PubMed

Xu, Limei; Zhang, Ying; Fan, Hui; Hu, Junhui; Yang, Jiashi

2009-03-01

We perform a theoretical analysis on a ceramic plate piezoelectric transformer operating with thickness-shear modes. Mindlin's first-order theory of piezoelectric plates is employed, and a forced vibration solution is obtained. Transforming ratio, resonant frequencies, and vibration mode shapes are calculated, and the effects of plate thickness and electrode dimension are examined.

Light pollution is associated with earlier tree budburst across the United Kingdom.

PubMed

Ffrench-Constant, Richard H; Somers-Yeates, Robin; Bennie, Jonathan; Economou, Theodoros; Hodgson, David; Spalding, Adrian; McGregor, Peter K

2016-06-29

The ecological impact of night-time lighting is of concern because of its well-demonstrated effects on animal behaviour. However, the potential of light pollution to change plant phenology and its corresponding knock-on effects on associated herbivores are less clear. Here, we test if artificial lighting can advance the timing of budburst in trees. We took a UK-wide 13 year dataset of spatially referenced budburst data from four deciduous tree species and matched it with both satellite imagery of night-time lighting and average spring temperature. We find that budburst occurs up to 7.5 days earlier in brighter areas, with the relationship being more pronounced for later-budding species. Excluding large urban areas from the analysis showed an even more pronounced advance of budburst, confirming that the urban 'heat-island' effect is not the sole cause of earlier urban budburst. Similarly, the advance in budburst across all sites is too large to be explained by increases in temperature alone. This dramatic advance of budburst illustrates the need for further experimental investigation into the impact of artificial night-time lighting on plant phenology and subsequent species interactions. As light pollution is a growing global phenomenon, the findings of this study are likely to be applicable to a wide range of species interactions across the world. © 2016 The Authors.

Sensory, physical and chemical characteristics of cooked ham manufactured from rapidly chilled and earlier deboned M. semimembranosus.

PubMed

Tomović, Vladimir M; Jokanović, Marija R; Petrović, Ljiljana S; Tomović, Mila S; Tasić, Tatjana A; Ikonić, Predrag M; Sumić, Zdravko M; Sojić, Branislav V; Skaljac, Snežana B; Sošo, Milena M

2013-01-01

Effects of rapid chilling of carcasses (at -31°C in the first 3h of chilling, and then at 2-4°C) and earlier deboning (8h post-mortem), compared to rapid (till 24h post-mortem) and conventional chilling (at 2-4°C, till 24h post-mortem), on quality characteristics of pork M. semimebranosus and cooked ham were investigated. Quality measurements included pH value, colour (CIEL a b values) and total aerobic count of M. semimebranosus, as well as sensory (colour, juiciness, texture, and flavour), physical (pH value, colour - CIEL a b values and texture - Warner-Bratzler shear and penetration forces) and chemical (protein, total fat, and moisture content) characteristics of cooked ham. The cooked ham was manufactured from pieces of M. semimebranosus with ultimate lightness (CIEL value) lower than 50. Rapid chilling and earlier deboning significantly increased quantity of M. semimebranosus desirable for cooked ham manufacturing. Earlier start of pork fabrication did not affect important quality characteristics of cooked ham. Copyright © 2012 Elsevier Ltd. All rights reserved.

Do theoretical calculations really predict nodes in Fe-based superconductors?

NASA Astrophysics Data System (ADS)

Mazin, Igor

2011-03-01

It is well established that calculations based on the LDA band structure and the Hubbard model, with the parameters U ~ 1.3 - 1.6 eV, and J ~ 0.2 - 0.3 J (a ``UJ'' model), yield strongly anisotropic, and sometimes nodal gaps. The physical origin of this effect is well understood: the two leading terms in the model are ∑Uni ↑ni ↓ and ∑ ' Uninj . The former ensures that the coupling to spin fluctuations proceeds only through the like orbitals, and the latter, not being renormalized by the standard Tolmachev-Morel-Anderson logarithm, tends to equalize the positive and the negative order parameters. Both these features are suspect on a general physics basis: the leading magnetic interaction in itinerant systems is the Hund-rule coupling, which couples every orbital with all the others, and the pnictides, with the order parameter less than 20 meV, should have nearly as strong renormalization of the Coulomb pseudopotential as the conventional superconductors. I will argue that, instead of the UJ model, in pnictides one should use the ``I'' model, derived from the density functional theory (which is supposed to describe the static susceptibility on the mean field level very accurately). The ``I'' here is simply the Stoner factor, the second variation of the LSDA magnetic energy. Unfortunately, this approach is very unlikely to produce gap nodes as easily as the UJ model, indicating that one has to look elsewhere for the nodes origin.

Trends of earlier palliative care consultation in advanced cancer patients receiving palliative radiation therapy.

PubMed

Chang, Sanders; Sigel, Keith; Goldstein, Nathan E; Wisnivesky, Juan; Dharmarajan, Kavita V

2018-06-06

The American Society of Clinical Oncology recommends that all patients with metastatic disease receive dedicated palliative care (PC) services early in their illness, ideally via interdisciplinary care teams. We investigated the time trends of specialty palliative care consultations from the date of metastatic cancer diagnosis among patients receiving palliative radiation therapy (PRT). A shorter time interval between metastatic diagnosis and first PC consultation suggests earlier involvement of palliative care in a patient's life with metastatic cancer. In this IRB-approved retrospective analysis, patients treated with PRT for solid tumors (bone and brain) at a single tertiary care hospital between 2010 and 2016 were included. Cohorts were arbitrarily established by metastatic diagnosis within approximately two-year intervals: (1) 1/1/2010-3/27/2012; (2) 3/28/2012-5/21/2014; and (3) 5/22/2014-12/31/2016. Cox-proportional hazards regression modelling was used to compare trends of PC consultation among cohorts. Of 284 patients identified, 184 patients received PC consultation, whereas 15 patients died before receiving a PC consult. Median follow-up time until an event or censor was 257 days (range: 1,900). Patients in the most recent cohort had a shorter median time to first PC consult (57 days) compared to those in the first (374 days) and second (186 days) cohorts. On multivariable analysis, patients in the third cohort were more likely to undergo a PC consultation earlier in their metastatic illness (HR: 1.8, 95% CI: 1.2,2.8). Over a six-year period, palliative care consultation occurred earlier for metastatic patients treated with PRT at our institution. Copyright © 2018. Published by Elsevier Inc.

Earlier time to aerobic exercise is associated with faster recovery following acute sport concussion.

PubMed

Lawrence, David Wyndham; Richards, Doug; Comper, Paul; Hutchison, Michael G

2018-01-01

To determine whether earlier time to initiation of aerobic exercise following acute concussion is associated with time to full return to (1) sport and (2) school or work. A retrospective stratified propensity score survival analysis of acute (≤14 days) concussion was used to determine whether time (days) to initiation of aerobic exercise post-concussion was associated with, both, time (days) to full return to (1) sport and (2) school or work. A total of 253 acute concussions [median (IQR) age, 17.0 (15.0-20.0) years; 148 (58.5%) males] were included in this study. Multivariate Cox regression models identified that earlier time to aerobic exercise was associated with faster return to sport and school/work adjusting for other covariates, including quintile propensity strata. For each successive day in delay to initiation of aerobic exercise, individuals had a less favourable recovery trajectory. Initiating aerobic exercise at 3 and 7 days following injury was associated with a respective 36.5% (HR, 0.63; 95% CI, 0.53-0.76) and 73.2% (HR, 0.27; 95% CI, 0.16-0.45) reduced probability of faster full return to sport compared to within 1 day; and a respective 45.9% (HR, 0.54; 95% CI, 0.44-0.66) and 83.1% (HR, 0.17; 95% CI, 0.10-0.30) reduced probability of faster full return to school/work. Additionally, concussion history, symptom severity, LOC deleteriously influenced concussion recovery. Earlier initiation of aerobic exercise was associated with faster full return to sport and school or work. This study provides greater insight into the benefits and safety of aerobic exercise within the first week of the injury.

Observed Barium Emission Rates

NASA Technical Reports Server (NTRS)

Stenbaek-Nielsen, H. C.; Wescott, E. M.; Hallinan, T. J.

1993-01-01

The barium releases from the CRRES satellite have provided an opportunity for verifying theoretically calculated barium ion and neutral emission rates. Spectra of the five Caribbean releases in the summer of 1991 were taken with a spectrograph on board a U.S. Air Force jet aircraft. Because the line of sight release densities are not known, only relative rates could be obtained. The observed relative rates agree well with the theoretically calculated rates and, together with other observations, confirm the earlier detailed theoretical emission rates. The calculated emission rates can thus with good accuracy be used with photometric observations. It has been postulated that charge exchange between neutral barium and oxygen ions represents a significant source for ionization. If so. it should be associated with emissions at 4957.15 A and 5013.00 A, but these emissions were not detected.

Spatial and Temporal Variation in Primary Productivity (NDVI) of Coastal Alaskan Tundra: Decreased Vegetation Growth Following Earlier Snowmelt

NASA Technical Reports Server (NTRS)

Gamon, John A.; Huemmrich, K. Fred; Stone, Robert S.; Tweedie, Craig E.

2015-01-01

In the Arctic, earlier snowmelt and longer growing seasons due to warming have been hypothesized to increase vegetation productivity. Using the Normalized Difference Vegetation Index (NDVI) from both field and satellite measurements as an indicator of vegetation phenology and productivity, we monitored spatial and temporal patterns of vegetation growth for a coastal wet sedge tundra site near Barrow, Alaska over three growing seasons (2000-2002). Contrary to expectation, earlier snowmelt did not lead to increased productivity. Instead, productivity was associated primarily with precipitation and soil moisture, and secondarily with growing degree days, which, during this period, led to reduced growth in years with earlier snowmelt. Additional moisture effects on productivity and species distribution, operating over a longer time scale, were evident in spatial NDVI patterns associated with microtopography. Lower, wetter regions dominated by graminoids were more productive than higher, drier locations having a higher percentage of lichens and mosses, despite the earlier snowmelt at the more elevated sites. These results call into question the oft-stated hypothesis that earlier arctic growing seasons will lead to greater vegetation productivity. Rather, they agree with an emerging body of evidence from recent field studies indicating that early-season, local environmental conditions, notably moisture and temperature, are primary factors determining arctic vegetation productivity. For this coastal arctic site, early growing season conditions are strongly influenced by microtopography, hydrology, and regional sea ice dynamics, and may not be easily predicted from snowmelt date or seasonal average air temperatures alone. Our comparison of field to satellite NDVI also highlights the value of in-situ monitoring of actual vegetation responses using field optical sampling to obtain detailed information on surface conditions not possible from satellite observations alone.

Neutrino oscillation processes in a quantum-field-theoretical approach

NASA Astrophysics Data System (ADS)

Egorov, Vadim O.; Volobuev, Igor P.

2018-05-01

It is shown that neutrino oscillation processes can be consistently described in the framework of quantum field theory using only the plane wave states of the particles. Namely, the oscillating electron survival probabilities in experiments with neutrino detection by charged-current and neutral-current interactions are calculated in the quantum field-theoretical approach to neutrino oscillations based on a modification of the Feynman propagator in the momentum representation. The approach is most similar to the standard Feynman diagram technique. It is found that the oscillating distance-dependent probabilities of detecting an electron in experiments with neutrino detection by charged-current and neutral-current interactions exactly coincide with the corresponding probabilities calculated in the standard approach.

Calculation of turbulence-driven secondary motion in ducts with arbitrary cross section

NASA Technical Reports Server (NTRS)

Demuren, A. O.

1989-01-01

Calculation methods for turbulent duct flows are generalized for ducts with arbitrary cross-sections. The irregular physical geometry is transformed into a regular one in computational space, and the flow equations are solved with a finite-volume numerical procedure. The turbulent stresses are calculated with an algebraic stress model derived by simplifying model transport equations for the individual Reynolds stresses. Two variants of such a model are considered. These procedures enable the prediction of both the turbulence-driven secondary flow and the anisotropy of the Reynolds stresses, in contrast to some of the earlier calculation methods. Model predictions are compared to experimental data for developed flow in triangular duct, trapezoidal duct and a rod-bundle geometry. The correct trends are predicted, and the quantitative agreement is mostly fair. The simpler variant of the algebraic stress model procured better agreement with the measured data.

Earlier nesting by generalist predatory bird is associated with human responses to climate change.

PubMed

Smith, Shawn H; Steenhof, Karen; McClure, Christopher J W; Heath, Julie A

2017-01-01

Warming temperatures cause temporal changes in growing seasons and prey abundance that drive earlier breeding by birds, especially dietary specialists within homogeneous habitat. Less is known about how generalists respond to climate-associated shifts in growing seasons or prey phenology, which may occur at different rates across land cover types. We studied whether breeding phenology of a generalist predator, the American kestrel (Falco sparverius), was associated with shifts in growing seasons and, presumably, prey abundance, in a mosaic of non-irrigated shrub/grasslands and irrigated crops/pastures. We examined the relationship between remotely-sensed normalized difference vegetation index (NDVI) and abundance of small mammals that, with insects, constitute approximately 93% of kestrel diet biomass. We used NDVI to estimate the start of the growing season (SoGS) in irrigated and non-irrigated lands from 1992 to 2015 and tested whether either estimate of annual SoGS predicted the timing of kestrel nesting. Finally, we examined relationships among irrigated SoGS, weather and crop planting. NDVI was a useful proxy for kestrel prey because it predicted small mammal abundance and past studies showed that NDVI predicts insect abundance. NDVI-estimated SoGS advanced significantly in irrigated lands (β = -1·09 ± 0·30 SE) but not in non-irrigated lands (β = -0·57 ± 0·53). Average date of kestrel nesting advanced 15 days in the past 24 years and was positively associated with the SoGS in irrigated lands, but not the SoGS in non-irrigated lands. Advanced SoGS in irrigated lands was related to earlier planting of crops after relatively warm winters, which were more common in recent years. Despite different patterns of SoGS change between land cover types, kestrel nesting phenology shifted with earlier prey availability in irrigated lands. Kestrels may preferentially track prey in irrigated lands over non-irrigated lands because of higher quality prey on

Structure of alcohol cluster ions in the gas phase, according to spectrometry and ab initio calculations

NASA Astrophysics Data System (ADS)

Krisilov, A. V.; Lantsuzskaya, E. V.; Levina, A. M.

2017-01-01

Reduced ion mobility and scattering cross sections are calculated from experimentally obtained spectra of the ion mobility of linear aliphatic alcohols with carbon atom numbers from 2 to 9. A linear increase in the scattering cross sections as the molecular weight grows is found. According to the results from experiments and quantum chemical calculations, alcohol cluster ions do not form a compact structure. Neither are dipole moments compensated for during dimerization, in contrast to the aldehydes and ketones described earlier. It was concluded from ab initio calculations that charge delocalization in monomeric and dimeric ions of alcohols increases the dipole moment many times over.

Recent gestational diabetes was associated with mothers stopping predominant breastfeeding earlier in a multi-ethnic population.

PubMed

Baerug, Anne; Sletner, Line; Laake, Petter; Fretheim, Atle; Løland, Beate Fossum; Waage, Christin W; Birkeland, Kåre I; Jenum, Anne Karen

2018-06-01

It has previously been shown that breastfeeding may reduce the risk of type 2 diabetes in mothers with recent gestational diabetes mellitus (GDM). This study compared the cessation of predominant breastfeeding in mothers with and without recent GDM in a multi-ethnic population. From May 2008 to May 2010, healthy pregnant women attending antenatal care provided by community health services in Eastern Oslo, Norway were recruited. We included 616 women-58% non-Western-and interviewed and examined them at a mean of 15 and 28 weeks of gestation and 14 weeks' postpartum. Cox regression models examined the association between GDM, as assessed by the 2013 World Health Organization criteria, and breastfeeding cessation. Overall, 190 of the 616 (31%) mothers had GDM and they ended predominant breastfeeding earlier than mothers without GDM, with an adjusted hazard ratio (aHR) of 1.33 and 95% confidence interval (95% CI) of 1.01-1.77. Mothers of South Asian origin ended predominant breastfeeding earlier than Western European mothers in the adjusted analysis (aHR 1.53, 95% CI: 1.04-2.25), but Middle Eastern mothers did not. Recent gestational diabetes was associated with earlier cessation of predominant breastfeeding in Western European and non-Western women. ©2018 Foundation Acta Paediatrica. Published by John Wiley & Sons Ltd.

Tidal Wave II Revisited: A Review of Earlier Enrollment Projections for California Higher Education.

ERIC Educational Resources Information Center

Hayward, Gerald C.; Breneman, David W.; Estrada, Leobardo F.

This report examined enrollment projections for higher education institutions in California in relation to earlier projections conducted in the mid-1990s that forecasted steep declines in enrollment. It notes that California's remarkable economic recovery over the last several years has allowed it to fund higher education enrollment growth at a…

Variations in a university subject pool as a function of earlier or later participation and self-report: a replication and extension.

PubMed

Bernard, Larry C; Walsh, R Patricia

2002-10-01

The present study replicated and extended earlier research on temporal sampling effects in university subject pools. Data were obtained from 236 participants, 79 men and 157 women, in a university subject pool during a 15-wk. semester. Without knowing the purpose of the study, participants self-selected to participate earlier (Weeks 4 and 5; n = 105) or later (Weeks 14 and 15; n = 131). Three hypotheses were investigated: (1) that the personality patterns of earlier and later participants on the NEO Personality Inventory-Revised and the Personality Research Form differ significantly, with earlier participants scoring higher on the latter scales reflecting social responsibility and higher on former Conscientiousness and Neuroticism scales; (2) that there are similar significant differences between participants in the earlier and later groups compared to the male and female college normative samples for the two tests: and (3) that earlier participants will have higher actual Scholastic Assessment Test scores and Grade Point Averages. Also investigated was whether participants' foreknowledge that their actual Scholastic Assessment Test scores and Grade Point Averages would be obtained would affect their accuracy of self-report. In contrast to prior research, neither the first nor second hypothesis was supported by the current study; there do not appear to be consistent differences on personality variables. However, the third hypothesis was supported. Earlier participants had higher actual high school Grade Point Average, college Grade Point Average, and Scholastic Assessment Test Verbal scores. Foreknowledge that actual Scholastic Assessment Test scores and Grade Point Averages would be obtained did not affect the accuracy of self-report. In addition, later participants significantly over-reported their scores, and significantly more women than men and more first-year than senior-year subjects participated in the early group.

Optical gain coefficients of silicon: a theoretical study

NASA Astrophysics Data System (ADS)

Tsai, Chin-Yi

2018-05-01

A theoretical model is presented and an explicit formula is derived for calculating the optical gain coefficients of indirect band-gap semiconductors. This model is based on the second-order time-dependent perturbation theory of quantum mechanics by incorporating all the eight processes of photon/phonon emission and absorption between the band edges of the conduction and valence bands. Numerical calculation results are given for Si. The calculated absorption coefficients agree well with the existing fitting formula of experiment data with two modes of phonons: optical phonons with energy of 57.73 meV and acoustic phonons with energy of 18.27 meV near (but not exactly at) the zone edge of the X-point in the dispersion relation of phonons. These closely match with existing data of 57.5 meV transverse optical (TO) phonons at the X4-point and 18.6 meV transverse acoustic (TA) phonons at the X3-point of the zone edge. The calculated results show that the material optical gain of Si will overcome free-carrier absorption if the energy separation of quasi-Fermi levels between electrons and holes exceeds 1.15 eV.

Higher Childhood Red Meat Intake Frequency Is Associated with Earlier Age at Menarche.

PubMed

Jansen, Erica C; Marín, Constanza; Mora-Plazas, Mercedes; Villamor, Eduardo

2016-03-09

Early age at menarche is associated with increased breast cancer risk. Red meat consumption in adolescence predicts breast cancer risk, but it is unknown whether it is also related to earlier menarche. We studied the association between intake of red meat at ages 5-12 y and age at menarche in a prospective study. We assessed usual diets with a food-frequency questionnaire in a group of 456 girls aged 8.4 ± 1.7 y and followed them for a median 5.6 y in Bogotá, Colombia. Girls were asked periodically about the occurrence and date of menarche. Median age at menarche was estimated with use of Kaplan-Meier survival probabilities by categories of red meat intake frequency. Cox proportional hazards models were used to compare the incidence of menarche by red meat intake frequency, adjusting for potential sociodemographic and dietary confounders including total energy intake and intake frequency of other animal food groups (dairy, poultry, freshwater fish, tuna/sardines, eggs, and innards). Median age at menarche was 12.4 y. After adjustment for total energy intake, maternal parity, and socioeconomic status, red meat intake frequency was inversely associated with age at menarche. When compared with girls with red meat intake <4 times/wk, those consuming it ≥2 times/d had a significantly earlier age at menarche (HR: 1.64; 95% CI: 1.11, 2.41; P-trend = 0.0009). Incidentally, we found that girls with tuna/sardine intake >1 time/wk had a significantly later age at menarche (HR: 0.62; 95% CI: 0.42, 0.90; P = 0.01) than those with intake <1 time/mo. Intake frequency of other animal food groups was not significantly associated with age at menarche. Higher red meat intake frequency during childhood is associated with an earlier age at menarche, whereas greater fatty fish intake frequency is associated with a later menarcheal age. © 2016 American Society for Nutrition.

Opacity Measurement and Theoretical Investigation of Hot Silicon Plasma

NASA Astrophysics Data System (ADS)

Xiong, Gang; Yang, Jiamin; Zhang, Jiyan; Hu, Zhimin; Zhao, Yang; Qing, Bo; Yang, Guohong; Wei, Minxi; Yi, Rongqing; Song, Tianming; Li, Hang; Yuan, Zheng; Lv, Min; Meng, Xujun; Xu, Yan; Wu, Zeqing; Yan, Jun

2016-01-01

We report on opacity measurements of a silicon (Si) plasma at a temperature of (72 ± 5) eV and a density of (6.0 ± 1.2) mg cm-3 in the photon energy range of 1790-1880 eV. A 23 μg cm-2 Si foil tamped by 50 μg cm-2 CH layers on each side was heated to a hot-dense plasma state by X-ray radiation emitted from a D-shaped gold cavity that was irradiated by intense lasers. Absorption lines of 1s - 2p transitions of Si xiii to Si ix ions have been measured using point-projection spectroscopy. The transmission spectrum of the silicon plasma was determined by comparing the light passing through the plasma to the light from the same shot passing by the plasma. The density of the Si plasma was determined experimentally by side-on radiography and the temperature was estimated from the radiation flux data. Radiative hydrodynamic simulations were performed to obtain the temporal evolutions of the density and temperature of the Si plasma. The experimentally obtained transmission spectra of the Si sample plasma have been reproduced using a detailed term account model with the local thermodynamic equilibrium approximation. The energy levels, oscillator strengths and photoionization cross-sections used in the calculation were generated by the flexible atomic code. The experimental transmission spectrum was compared with the theoretical calculation and good agreement was found. The present experimental spectrum and theoretical calculation were also compared with the new opacities available in the Los Alamos OPLIB database.

Structural, Electronic and Dynamical Properties of Curium Monopnictides: Density Functional Calculations

NASA Astrophysics Data System (ADS)

Roondhe, Basant; Upadhyay, Deepak; Som, Narayan; Pillai, Sharad B.; Shinde, Satyam; Jha, Prafulla K.

2017-03-01

The structural, electronic, dynamical and thermodynamical properties of CmX (X = N, P, As, Sb, and Bi) compounds are studied using first principles calculations within density functional theory. The Perdew-Burke-Ernzerhof spin polarized generalized gradient approximation and Perdew-Wang (PW) spin polarized local density approximation as the exchange correlational functionals are used in these calculations. There is a good agreement between the present and previously reported data. The calculated electronic density of states suggests that the curium monopnictides are metallic in nature, which is consistent with earlier studies. The significant values of magnetic moment suggest their magnetic nature. The phonon dispersion curves and phonon density of states are also calculated, which depict the dynamical stability of these compounds. There is a significant separation between the optical and acoustical phonon branches. The temperature dependence of the thermodynamical functions are also calculated and discussed. Internal energy and vibrational contribution to the Helmholtz free energy increases and decreases, respectively, with temperature. The entropy increases with temperature. The specific heat at constant volume and Debye temperature obey Debye theory. The temperature variation of the considered thermodynamical functions is in line with those of other crystalline solids.

Calculations of Hubbard U from first-principles

NASA Astrophysics Data System (ADS)

Aryasetiawan, F.; Karlsson, K.; Jepsen, O.; Schönberger, U.

2006-09-01

The Hubbard U of the 3d transition metal series as well as SrVO3 , YTiO3 , Ce, and Gd has been estimated using a recently proposed scheme based on the random-phase approximation. The values obtained are generally in good accord with the values often used in model calculations but for some cases the estimated values are somewhat smaller than those used in the literature. We have also calculated the frequency-dependent U for some of the materials. The strong frequency dependence of U in some of the cases considered in this paper suggests that the static value of U may not be the most appropriate one to use in model calculations. We have also made comparison with the constrained local density approximation (LDA) method and found some discrepancies in a number of cases. We emphasize that our scheme and the constrained local density approximation LDA method theoretically ought to give similar results and the discrepancies may be attributed to technical difficulties in performing calculations based on currently implemented constrained LDA schemes.

Theoretical and experimental characterization of the first hyperpolarizability

NASA Astrophysics Data System (ADS)

Perez-Moreno, Javier

We present a theoretical and experimental study of the molecular susceptibilities. The generalized Thomas-Kuhn sum rules are used to characterize the nonlinear response of organic chromophores in terms of fundamental parameters. The nonlinear optical performance of real molecules is evaluated from the calculation of the quantum limits and Hyper-Rayleigh scattering measurements. Different strategies for the enhancement of nonlinear behavior at the molecular and supramolecular level are evaluated and new paradigms for de design of more efficient nonlinear molecules are proposed.

Combine experimental and theoretical investigation on an alkaloid-Dimethylisoborreverine

NASA Astrophysics Data System (ADS)

Singh, Swapnil; Singh, Harshita; Karthick, T.; Agarwal, Parag; Erande, Rohan D.; Dethe, Dattatraya H.; Tandon, Poonam

2016-01-01

A combined experimental (FT-IR, 1H and 13C NMR) and theoretical approach is used to study the structure and properties of antimalarial drug dimethylisoborreverine (DMIB). Conformational analysis, has been performed by plotting one dimensional potential energy curve that was computed using density functional theory (DFT) with B3LYP/6-31G method and predicted conformer A1 as the most stable conformer. After full geometry optimization, harmonic wavenumbers were computed for conformer A1 at the DFT/B3LYP/6-311++G(d,P) level. A complete vibrational assignment of all the vibrational modes have been performed on the bases of the potential energy distribution (PED) and theoretical results were found to be in good agreement with the observed data. To predict the solvent effect, the UV-Vis spectra were calculated in different solvents by polarizable continuum model using TD-DFT method. Molecular docking studies were performed to test the biological activity of the sample using SWISSDOCK web server and Hex 8.0.0 software. The molecular electrostatic potential (MESP) was plotted to identify the reactive sites of the molecule. Natural bond orbital (NBO) analysis was performed to get a deep insight of intramolecular charge transfer. Thermodynamical parameters were calculated to predict the direction of chemical reaction.

Theoretical and experimental study on electron interactions with chlorobenzene: Shape resonances and differential cross sections

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

Barbosa, Alessandra Souza; Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica; Varella, Márcio T. do N.

2016-08-28

In this work, we report theoretical and experimental cross sections for elastic scattering of electrons by chlorobenzene (ClB). The theoretical integral and differential cross sections (DCSs) were obtained with the Schwinger multichannel method implemented with pseudopotentials (SMCPP) and the independent atom method with screening corrected additivity rule (IAM-SCAR). The calculations with the SMCPP method were done in the static-exchange (SE) approximation, for energies above 12 eV, and in the static-exchange plus polarization approximation, for energies up to 12 eV. The calculations with the IAM-SCAR method covered energies up to 500 eV. The experimental differential cross sections were obtained in themore » high resolution electron energy loss spectrometer VG-SEELS 400, in Lisbon, for electron energies from 8.0 eV to 50 eV and angular range from 7{sup ∘} to 110{sup ∘}. From the present theoretical integral cross section (ICS) we discuss the low-energy shape-resonances present in chlorobenzene and compare our computed resonance spectra with available electron transmission spectroscopy data present in the literature. Since there is no other work in the literature reporting differential cross sections for this molecule, we compare our theoretical and experimental DCSs with experimental data available for the parent molecule benzene.« less

Clinical presentation of retinoblastoma in Alexandria: A step toward earlier diagnosis.

PubMed

Soliman, Sameh E; Eldomiaty, Wesam; Goweida, Mohamed B; Dowidar, Amgad

2017-01-01

To evaluate the clinical presentation of retinoblastoma in Alexandria, Egypt, correlate the timing of accurate diagnosis with the presence of advanced disease and identify causes of delayed presentation. Retrospective noncomparative single institution study reviews demographic and clinical data of all new children with retinoblastoma presenting to Alexandria Main University ocular oncology clinic (OOC) from January 2012 to June 2014. Diagnosis time was from initial parental complaint to retinoblastoma diagnosis and referral time was from retinoblastoma diagnosis to presentation to the Alexandria OCC. Delayed Diagnosis and referral were counted if >2 weeks. Advanced presentation is defined as clinical TNMH (8th edition) staging of cT2 or cT3 (international intraocular retinoblastoma classification group D or E) in at least one eye or the presence of extra-ocular disease (cT4). Seventy eyes of 47 children were eligible: 52% unilateral, 7% with family history and 96% presented with leukocorea. Sixty-four percent of children had advanced intraocular disease and none had extra-ocular disease. Delayed presentation occurred in 58% of children and was significantly associated with advanced disease in both unilaterally and bilaterally affected children (p = 0.003, 0.002 respectively). The delay in diagnosis was more in unilateral cases while the delay in referral was more in bilateral cases. The main cause of delayed presentation in unilateral retinoblastoma was misdiagnosis (30%) while parental shopping for second medical opinion (30%) was the main cause in bilateral children. Delayed diagnosis is a problem affecting retinoblastoma management. Better medical education and training, health education and earlier screening are recommended to achieve earlier diagnosis.

Spectral and structural studies of the anti-cancer drug Flutamide by density functional theoretical method.

PubMed

Mariappan, G; Sundaraganesan, N

2014-01-03

A comprehensive screening of the more recent DFT theoretical approach to structural analysis is presented in this section of theoretical structural analysis. The chemical name of 2-methyl-N-[4-nitro-3-(trifluoromethyl)phenyl]-propanamide is usually called as Flutamide (In the present study it is abbreviated as FLT) and is an important and efficacious drug in the treatment of anti-cancer resistant. The molecular geometry, vibrational spectra, electronic and NMR spectral interpretation of Flutamide have been studied with the aid of density functional theory method (DFT). The vibrational assignments of the normal modes were performed on the basis of the PED calculations using the VEDA 4 program. Comparison of computational results with X-ray diffraction results of Flutamide allowed the evaluation of structure predictions and confirmed B3LYP/6-31G(d,p) as accurate for structure determination. Application of scaling factors for IR and Raman frequency predictions showed good agreement with experimental values. This is supported the assignment of the major contributors of the vibration modes of the title compound. Stability of the molecule arising from hyperconjugative interactions leading to its bioactivity, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. NMR chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. The comparison of measured FTIR, FT-Raman, and UV-Visible data to calculated values allowed assignment of major spectral features of the title molecule. Besides, Frontier molecular orbital analyze was also investigated using theoretical calculations. Copyright © 2013 Elsevier B.V. All rights reserved.

Comparison between Theoretical Calculation and Experimental Results of Excitation Functions for Production of Relevant Biomedical Radionuclides

NASA Astrophysics Data System (ADS)

Menapace, E.; Birattari, C.; Bonardi, M. L.; Groppi, F.; Morzenti, S.; Zona, C.

2005-05-01

The radionuclide production for biomedical applications has been brought up in the years, as a special nuclear application, at INFN LASA Laboratory, particularly in co-operation with the JRC-Ispra of EC. Mainly scientific aspects concerning radiation detection and the relevant instruments, the measurements of excitation functions of the involved nuclear reactions, the requested radiochemistry studies and further applications have been investigated. On the side of the nuclear data evaluations, based on nuclear model calculations and critically selected experimental data, the appropriate competence has been developed at ENEA Division for Advanced Physics Technologies. A series of high specific activity accelerator-produced radionuclides in no-carrier-added (NCA) form, for uses in metabolic radiotherapy and for PET radiodiagnostics, are investigated. In this work, last revised measurements and model calculations are reviewed for excitation functions of natZn(d,X)64Cu, 66Ga reactions, referring to irradiation experiments at K=38 variable energy Cyclotron of JRC-Ispra. Concerning the reaction data for producing 186gRe and 211At/211gPo (including significant emission spectra) and 210At, most recent and critically selected experimental results are considered and discussed in comparison with model calculations paying special care to pre-equilibrium effects estimate and to the appropriate overall parameterization. Model calculations are presented for 226Ra(p,2n)225Ac reaction, according to the working program of the ongoing IAEA CRP on the matter.

Comparison between Theoretical Calculation and Experimental Results of Excitation Functions for Production of Relevant Biomedical Radionuclides

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

Menapace, E.; Birattari, C.; Bonardi, M.L.

The radionuclide production for biomedical applications has been brought up in the years, as a special nuclear application, at INFN LASA Laboratory, particularly in co-operation with the JRC-Ispra of EC. Mainly scientific aspects concerning radiation detection and the relevant instruments, the measurements of excitation functions of the involved nuclear reactions, the requested radiochemistry studies and further applications have been investigated. On the side of the nuclear data evaluations, based on nuclear model calculations and critically selected experimental data, the appropriate competence has been developed at ENEA Division for Advanced Physics Technologies. A series of high specific activity accelerator-produced radionuclides inmore » no-carrier-added (NCA) form, for uses in metabolic radiotherapy and for PET radiodiagnostics, are investigated. In this work, last revised measurements and model calculations are reviewed for excitation functions of natZn(d,X)64Cu, 66Ga reactions, referring to irradiation experiments at K=38 variable energy Cyclotron of JRC-Ispra. Concerning the reaction data for producing 186gRe and 211At/211gPo (including significant emission spectra) and 210At, most recent and critically selected experimental results are considered and discussed in comparison with model calculations paying special care to pre-equilibrium effects estimate and to the appropriate overall parameterization. Model calculations are presented for 226Ra(p,2n)225Ac reaction, according to the working program of the ongoing IAEA CRP on the matter.« less

Theoretical study of modulated multi-layer SPR device for improved refractive index sensing

NASA Astrophysics Data System (ADS)

Mohapatra, Saswat; Moirangthem, Rakesh S.

2018-02-01

In the present work, a theoretical investigation of Surface Plasmon Resonance (SPR) properties of a multilayer film (Au-SiO2-Au) coated on a glass prism is being carried out. In this multilayer structure, each interface corresponds to multiple SPR modes. To obtain the maximum reflection dips in the SPR modes, the thickness of SiO2 layer is optimized by varying it from 100-600 nm. Our calculation also reveals that SPR mode corresponding to Au-ambient interface is very sensitive to the changes in the surrounding medium, least affecting other SPR modes. The sensing performance of the proposed nano-plasmonic sensor is theoretically calculated using bulk refractive index sensing. Such multilayer SPR sensing device has advantages over conventional SPR devices in terms of their bulk sensitivity and self-referencing, claiming itself as a potential candidate for the development of highly sensitive biological sensor.

A submerged singularity method for calculating potential flow velocities at arbitrary near-field points

NASA Technical Reports Server (NTRS)

Maskew, B.

1976-01-01

A discrete singularity method has been developed for calculating the potential flow around two-dimensional airfoils. The objective was to calculate velocities at any arbitrary point in the flow field, including points that approach the airfoil surface. That objective was achieved and is demonstrated here on a Joukowski airfoil. The method used combined vortices and sources ''submerged'' a small distance below the airfoil surface and incorporated a near-field subvortex technique developed earlier. When a velocity calculation point approached the airfoil surface, the number of discrete singularities effectively increased (but only locally) to keep the point just outside the error region of the submerged singularity discretization. The method could be extended to three dimensions, and should improve nonlinear methods, which calculate interference effects between multiple wings, and which include the effects of force-free trailing vortex sheets. The capability demonstrated here would extend the scope of such calculations to allow the close approach of wings and vortex sheets (or vortices).

An experimental and theoretical core-level study of tautomerism in guanine.

PubMed

Plekan, Oksana; Feyer, Vitaliy; Richter, Robert; Coreno, Marcello; Vall-Llosera, Gemma; Prince, Kevin C; Trofimov, Alexander B; Zaytseva, Irina L; Moskovskaya, Tatyana E; Gromov, Evgeniy V; Schirmer, Jochen

2009-08-20

The core level photoemission and near edge X-ray photoabsorption spectra of guanine in the gas phase have been measured and the results interpreted with the aid of high level ab initio calculations. Tautomers are clearly identified spectroscopically, and their relative free energies and Boltzmann populations at the temperature of the experiment (600 K) have been calculated and compared with the experimental results and with previous calculations. We obtain good agreement between experiment and the Boltzmann weighted theoretical photoemission spectra, which allows a quantitative determination of the ratio of oxo to hydroxy tautomer populations. For the photoabsorption spectra, good agreement is found for the C 1s and O 1s spectra but only fair agreement for the N 1s edge.

Theoretical face pressure and drag characteristics of forward-facing steps in supersonic turbulent boundary layers

NASA Technical Reports Server (NTRS)

Patel, D. K.; Czarnecki, K. R.

1975-01-01

A theoretical investigation of the pressure distributions and drag characteristics was made for forward facing steps in turbulent flow at supersonic speeds. An approximate solution technique proposed by Uebelhack has been modified and extended to obtain a more consistent numerical procedure. A comparison of theoretical calculations with experimental data generally indicated good agreement over the experimentally available range of ratios of step height to boundary layer thickness from 7 to 0.05.

Experimental and Theoretical Research on the Compression Performance of CFRP Sheet Confined GFRP Short Pipe

PubMed Central

Zhao, Qilin; Chen, Li; Shao, Guojian

2014-01-01

The axial compressive strength of unidirectional FRP made by pultrusion is generally quite lower than its axial tensile strength. This fact decreases the advantages of FRP as main load bearing member in engineering structure. A theoretical iterative calculation approach was suggested to predict the ultimate axial compressive stress of the combined structure and analyze the influences of geometrical parameters on the ultimate axial compressive stress of the combined structure. In this paper, the experimental and theoretical research on the CFRP sheet confined GFRP short pole was extended to the CFRP sheet confined GFRP short pipe, namely, a hollow section pole. Experiment shows that the bearing capacity of the GFRP short pipe can also be heightened obviously by confining CFRP sheet. The theoretical iterative calculation approach in the previous paper is amended to predict the ultimate axial compressive stress of the CFRP sheet confined GFRP short pipe, of which the results agree with the experiment. Lastly the influences of geometrical parameters on the new combined structure are analyzed. PMID:24672288

Earlier time to aerobic exercise is associated with faster recovery following acute sport concussion

PubMed Central

Richards, Doug; Comper, Paul; Hutchison, Michael G.

2018-01-01

Objective To determine whether earlier time to initiation of aerobic exercise following acute concussion is associated with time to full return to (1) sport and (2) school or work. Methods A retrospective stratified propensity score survival analysis of acute (≤14 days) concussion was used to determine whether time (days) to initiation of aerobic exercise post-concussion was associated with, both, time (days) to full return to (1) sport and (2) school or work. Results A total of 253 acute concussions [median (IQR) age, 17.0 (15.0–20.0) years; 148 (58.5%) males] were included in this study. Multivariate Cox regression models identified that earlier time to aerobic exercise was associated with faster return to sport and school/work adjusting for other covariates, including quintile propensity strata. For each successive day in delay to initiation of aerobic exercise, individuals had a less favourable recovery trajectory. Initiating aerobic exercise at 3 and 7 days following injury was associated with a respective 36.5% (HR, 0.63; 95% CI, 0.53–0.76) and 73.2% (HR, 0.27; 95% CI, 0.16–0.45) reduced probability of faster full return to sport compared to within 1 day; and a respective 45.9% (HR, 0.54; 95% CI, 0.44–0.66) and 83.1% (HR, 0.17; 95% CI, 0.10–0.30) reduced probability of faster full return to school/work. Additionally, concussion history, symptom severity, LOC deleteriously influenced concussion recovery. Conclusion Earlier initiation of aerobic exercise was associated with faster full return to sport and school or work. This study provides greater insight into the benefits and safety of aerobic exercise within the first week of the injury. PMID:29668716

Factors associated with late diagnosis of HIV infection and missed opportunities for earlier testing.

PubMed

Gullón, Alejandra; Verdejo, José; de Miguel, Rosa; Gómez, Ana; Sanz, Jesús

2016-10-01

Late diagnosis (LD) of human immunodeficiency virus (HIV) infection continues to be a significant problem that increases disease burden both for patients and for the public health system. Guidelines have been updated in order to facilitate earlier HIV diagnosis, introducing "indicator condition-guided HIV testing". In this study, we analysed the frequency of LD and associated risk factors. We retrospectively identified those cases that could be considered missed opportunities for an earlier diagnosis. All patients newly diagnosed with HIV infection who attended Hospital La Princesa, Madrid (Spain) between 2007 and 2014 were analysed. We collected epidemiological, clinical and immunological data. We also reviewed electronic medical records from the year before the HIV diagnosis to search for medical consultations due to clinical indicators. HIV infection was diagnosed in 354 patients. The median CD4 count at presentation was 352 cells/mm(3). Overall, 158 patients (50%) met the definition of LD, and 97 (30.7%) the diagnosis of advanced disease. LD was associated with older age and was more frequent amongst immigrants. Heterosexual relations and injection drug use were more likely to be the reasons for LD than relations between men who have sex with men. During the year preceding the diagnosis, 46.6% of the patients had sought medical advice owing to the presence of clinical indicators that should have led to HIV testing. Of those, 24 cases (14.5%) were classified as missed opportunities for earlier HIV diagnosis because testing was not performed. According to these results, all health workers should pursue early HIV diagnosis through the proper implementation of HIV testing guidelines. Such an approach would prove directly beneficial to the patient and indirectly beneficial to the general population through the reduction in the risk of transmission.

Falling Chains as Variable-Mass Systems: Theoretical Model and Experimental Analysis

ERIC Educational Resources Information Center

de Sousa, Celia A.; Gordo, Paulo M.; Costa, Pedro

2012-01-01

In this paper, we revisit, theoretically and experimentally, the fall of a folded U-chain and of a pile-chain. The model calculation implies the division of the whole system into two subsystems of variable mass, allowing us to explore the role of tensional contact forces at the boundary of the subsystems. This justifies, for instance, that the…

Commentary on factors affecting transverse vibration using an idealized theoretical equation

Treesearch

Joseph F. Murphy

2000-01-01

An idealized theoretical equation to calculate flexural stiffness using transverse vibration of a simply end-supported beam is being considered by the American Society of Testing and Materials (ASTM) Wood Committee D07 to determine lumber modulus of elasticity. This commentary provides the user a quantitative view of six factors that affect the accuracy of using the...

An experimental and theoretical investigation into the electronically excited states of para-benzoquinone

NASA Astrophysics Data System (ADS)

Jones, D. B.; Limão-Vieira, P.; Mendes, M.; Jones, N. C.; Hoffmann, S. V.; da Costa, R. F.; Varella, M. T. do N.; Bettega, M. H. F.; Blanco, F.; García, G.; Ingólfsson, O.; Lima, M. A. P.; Brunger, M. J.

2017-05-01

We report on a combination of experimental and theoretical investigations into the structure of electronically excited para-benzoquinone (pBQ). Here synchrotron photoabsorption measurements are reported over the 4.0-10.8 eV range. The higher resolution obtained reveals previously unresolved pBQ spectral features. Time-dependent density functional theory calculations are used to interpret the spectrum and resolve discrepancies relating to the interpretation of the Rydberg progressions. Electron-impact energy loss experiments are also reported. These are combined with elastic electron scattering cross section calculations performed within the framework of the independent atom model-screening corrected additivity rule plus interference (IAM-SCAR + I) method to derive differential cross sections for electronic excitation of key spectral bands. A generalized oscillator strength analysis is also performed, with the obtained results demonstrating that a cohesive and reliable quantum chemical structure and cross section framework has been established. Within this context, we also discuss some issues associated with the development of a minimal orbital basis for the single configuration interaction strategy to be used for our high-level low-energy electron scattering calculations that will be carried out as a subsequent step in this joint experimental and theoretical investigation.

Examining Graphing Calculator Affordances in Learning Pre-Calculus among Undergraduate Students

ERIC Educational Resources Information Center

Nzuki, Francis

2016-01-01

This study examines graphing calculator affordances in learning mathematics among college precalculus students. The study draws from the Cognitive Load Theory (CLT) and the "Intelligent Technology" theoretical framework proposed by Salomon, Perkins, and Globerson (1991). From these perspectives the effects "with" the graphing…

A new simple local muscle recovery model and its theoretical and experimental validation.

PubMed

Ma, Liang; Zhang, Wei; Wu, Su; Zhang, Zhanwu

2015-01-01

This study was conducted to provide theoretical and experimental validation of a local muscle recovery model. Muscle recovery has been modeled in different empirical and theoretical approaches to determine work-rest allowance for musculoskeletal disorder (MSD) prevention. However, time-related parameters and individual attributes have not been sufficiently considered in conventional approaches. A new muscle recovery model was proposed by integrating time-related task parameters and individual attributes. Theoretically, this muscle recovery model was compared to other theoretical models mathematically. Experimentally, a total of 20 subjects participated in the experimental validation. Hand grip force recovery and shoulder joint strength recovery were measured after a fatiguing operation. The recovery profile was fitted by using the recovery model, and individual recovery rates were calculated as well after fitting. Good fitting values (r(2) > .8) were found for all the subjects. Significant differences in recovery rates were found among different muscle groups (p < .05). The theoretical muscle recovery model was primarily validated by characterization of the recovery process after fatiguing operation. The determined recovery rate may be useful to represent individual recovery attribute.

Faddeev calculations of. pi. D scattering

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

Thomas, A.W.

1976-01-01

The present status of the Faddeev calculations of ..pi..D scattering is summarized, with emphasis on what has been learned about common approximation methods (for ..pi..-nucleus as well as ..pi..D). Some space is devoted to a discussion of the theoretical work which remains, including a suggestion of co-operation between theorists on a ''homework'' problem. Finally, examples of the interesting phenomena are given which one hopes to investigate through good ..pi..D experiments. Suggestions are made as to which experiments would be most useful.

Theoretical and Observational Studies of Meteor Interactions with the Ionosphere

DTIC Science & Technology

2006-06-01

within an order of magnitude. The histograms of scattering mass, calculated from data collected at the ALTAIR rada are contained in Figure 1 . These...RTO-MP-IST-056 12 - 1 UNCLASSIFIED/UNLIMITED UNCLASSIFIED/UNLIMITED Theoretical and Observational Studies of Meteor Interactions with the...Observational Studies of Meteor Interactions with the Ionosphere. In Characterising the Ionosphere (pp. 12- 1 – 12-12). Meeting Proceedings RTO-MP-IST-056

Theoretical Estimate of Maximum Possible Nuclear Explosion

DOE R&D Accomplishments Database

Bethe, H. A.

1950-01-31

The maximum nuclear accident which could occur in a Na-cooled, Be moderated, Pu and power producing reactor is estimated theoretically. (T.R.H.) 2O82 Results of nuclear calculations for a variety of compositions of fast, heterogeneous, sodium-cooled, U-235-fueled, plutonium- and power-producing reactors are reported. Core compositions typical of plate-, pin-, or wire-type fuel elements and with uranium as metal, alloy, and oxide were considered. These compositions included atom ratios in the following range: U-23B to U-235 from 2 to 8; sodium to U-235 from 1.5 to 12; iron to U-235 from 5 to 18; and vanadium to U-235 from 11 to 33. Calculations were performed to determine the effect of lead and iron reflectors between the core and blanket. Both natural and depleted uranium were evaluated as the blanket fertile material. Reactors were compared on a basis of conversion ratio, specific power, and the product of both. The calculated results are in general agreement with the experimental results from fast reactor assemblies. An analysis of the effect of new cross-section values as they became available is included. (auth)

Good Practices in Free-energy Calculations

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Jarzynski, Christopher; Chipot, Christopher

2013-01-01

As access to computational resources continues to increase, free-energy calculations have emerged as a powerful tool that can play a predictive role in drug design. Yet, in a number of instances, the reliability of these calculations can be improved significantly if a number of precepts, or good practices are followed. For the most part, the theory upon which these good practices rely has been known for many years, but often overlooked, or simply ignored. In other cases, the theoretical developments are too recent for their potential to be fully grasped and merged into popular platforms for the computation of free-energy differences. The current best practices for carrying out free-energy calculations will be reviewed demonstrating that, at little to no additional cost, free-energy estimates could be markedly improved and bounded by meaningful error estimates. In energy perturbation and nonequilibrium work methods, monitoring the probability distributions that underlie the transformation between the states of interest, performing the calculation bidirectionally, stratifying the reaction pathway and choosing the most appropriate paradigms and algorithms for transforming between states offer significant gains in both accuracy and precision. In thermodynamic integration and probability distribution (histogramming) methods, properly designed adaptive techniques yield nearly uniform sampling of the relevant degrees of freedom and, by doing so, could markedly improve efficiency and accuracy of free energy calculations without incurring any additional computational expense.

Theoretical study on the dissociation energies, ionization potentials and electron affinities of three perfluoroalkyl iodides

NASA Astrophysics Data System (ADS)

Cheng, Li; Shen, Zuochun; Lu, Jianye; Gao, Huide; Lü, Zhiwei

2005-11-01

Dissociation energies, ionization potentials and electron affinities of three perfluoroalkyl iodides, CF 3I, C 2F 5I, and i-C 3F 7I are calculated accurately with B3LYP, MP n ( n = 2-4), QCISD, QCISD(T), CCSD, and CCSD(T) methods. Calculations are performed by using large-core correlation-consistent pseudopotential basis set (SDB-aug-cc-pVTZ) for iodine atom. In all energy calculations, the zero point vibration energy is corrected. And the basis set superposition error is corrected by counterpoise method in the calculation of dissociation energy. Theoretical results are compared with the experimental values.

Theoretical study of diaquamalonatozinc(II) single crystal for applications in non-linear optical devices

NASA Astrophysics Data System (ADS)

Chakraborty, Mitesh; Rai, Vineet Kumar

2017-12-01

The aim of the present paper is to employ theoretical methods to investigate the zero field splitting (ZFS) parameter and to investigate the position of the dopant in the host. These theoretical calculations have been compared with the empirical results. The superposition model (SPM) with the microscopic spin-Hamiltonian (MSH) theory and the coefficient of fractional parentage have been employed to investigate the dopant manganese(II) ion substitution in the diaquamalonatozinc(II) (DAMZ) single crystal. The magnetic parameters, viz. g-tensor and D-tensor, has been determined by using the ORCA program package developed by F Neese et al. The unrestricted Kohn-Sham orbitals-based Pederson-Khanna (PK) as the unperturbed wave function is observed to be the most suitable for the computational calculation of spin-orbit tensor (D^{SO}) of the axial ZFS parameter D. The effects of spin-spin dipolar couplings are taken into account. The unrestricted natural orbital (UNO) is used for the calculation of spin-spin dipolar contributions to the ZFS tensor. A comparative study of the quantum mechanical treatment of Pederson-Khanna (PK) with coupled perturbation (CP) is reported in the present study. The unrestricted Kohn-Sham-based natural orbital with Pederson-Khanna-type of perturbation approach validates the experimental results in the evaluation of ZFS parameters. The theoretical results are appropriate with the experimental ones and indicate the interstitial occupancy of Mn^{2+} ion in the host matrix.

Theoretical modeling of yields for proton-induced reactions on natural and enriched molybdenum targets.

PubMed

Celler, A; Hou, X; Bénard, F; Ruth, T

2011-09-07

Recent acute shortage of medical radioisotopes prompted investigations into alternative methods of production and the use of a cyclotron and ¹⁰⁰Mo(p,2n)(99m)Tc reaction has been considered. In this context, the production yields of (99m)Tc and various other radioactive and stable isotopes which will be created in the process have to be investigated, as these may affect the diagnostic outcome and radiation dosimetry in human studies. Reaction conditions (beam and target characteristics, and irradiation and cooling times) need to be optimized in order to maximize the amount of (99m)Tc and minimize impurities. Although ultimately careful experimental verification of these conditions must be performed, theoretical calculations can provide the initial guidance allowing for extensive investigations at little cost. We report the results of theoretically determined reaction yields for (99m)Tc and other radioactive isotopes created when natural and enriched molybdenum targets are irradiated by protons. The cross-section calculations were performed using a computer program EMPIRE for the proton energy range 6-30 MeV. A computer graphical user interface for automatic calculation of production yields taking into account various reaction channels leading to the same final product has been created. The proposed approach allows us to theoretically estimate the amount of (99m)Tc and its ratio relative to (99g)Tc and other radioisotopes which must be considered reaction contaminants, potentially contributing to additional patient dose in diagnostic studies.

Molecular structure and vibrational spectra of Irinotecan: a density functional theoretical study.

PubMed

Chinna Babu, P; Sundaraganesan, N; Sudha, S; Aroulmoji, V; Murano, E

2012-12-01

The solid phase FTIR and FT-Raman spectra of Irinotecan have been recorded in the regions 400-4000 and 50-4000 cm(-1), respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The structure of the molecule was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(d) as basis set. The vibrational frequencies were calculated for Irinotecan by DFT method and were compared with the experimental frequencies, which yield good agreement between observed and calculated frequencies. The infrared spectrum was also simulated from the calculated intensities. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis were investigated using theoretical calculations. Copyright © 2012 Elsevier B.V. All rights reserved.

Theoretical prediction of honeycomb carbon as Li-ion batteries anode material

NASA Astrophysics Data System (ADS)

Hu, Junping; Zhang, Xiaohang

2018-05-01

First principles calculations are performed to study the electronic properties and Li storage capability of honeycomb carbon. We find its right model consistent with the experimental result, the honeycomb carbon and its Li-intercalated configurations are all metallic which is beneficial to the electrode materials for lithium-ion batteries. The model 1 configuration shows fast Li diffusion and theoretical Li storage capacity of 319 mAh/g. Moreover, the average intercalation potentials for honeycomb carbon material is calculated to be low relatively. Our results suggest that the honeycomb carbon would be a new promising pure carbon anode material for Li-ion batteries.

Return of hunger following a relatively high carbohydrate breakfast is associated with earlier recorded glucose peak and nadir

PubMed Central

Chandler-Laney, Paula C.; Morrison, Shannon A.; Goree, Laura Lee T.; Ellis, Amy C.; Casazza, Krista; Desmond, Renee; Gower, Barbara A

2014-01-01

Objective To test the hypothesis that a breakfast meal with high carbohydrate/ low fat results in an earlier increase in postprandial glucose and insulin, a greater decrease below baseline in postprandial glucose, and an earlier return of appetite, compared to a low carbohydrate/high fat meal. Design Overweight but otherwise healthy adults (n=64) were maintained on one of two eucaloric diets: high carbohydrate/low fat (HC/LF; 55:27:18% kcals from carbohydrate: fat: protein) versus low carbohydrate/high fat (LC/HF; 43:39:18% kcals from carbohydrate: fat: protein). After 4 weeks of acclimation to the diets, participants underwent a meal test during which circulating glucose and insulin and self-reported hunger and fullness, were measured before and after consumption of breakfast from their assigned diets. Results The LC/HF meal resulted in a later time at the highest and lowest recorded glucose, higher glucose concentrations at 3 and 4 hours post-meal, and lower insulin incremental area under the curve. Participants consuming the LC/HF meal reported lower appetite 3 and 4 hours following the meal, a response that was associated with the timing of the highest and lowest recorded glucose. Conclusions Modest increases in meal carbohydrate content at the expense of fat content may facilitate weight gain over the long-term by contributing to an earlier rise and fall of postprandial glucose concentrations and an earlier return of appetite. PMID:24819342

Quantum Monte Carlo Calculations Applied to Magnetic Molecules

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

Engelhardt, Larry

2006-01-01

We have calculated the equilibrium thermodynamic properties of Heisenberg spin systems using a quantum Monte Carlo (QMC) method. We have used some of these systems as models to describe recently synthesized magnetic molecules, and-upon comparing the results of these calculations with experimental data-have obtained accurate estimates for the basic parameters of these models. We have also performed calculations for other systems that are of more general interest, being relevant both for existing experimental data and for future experiments. Utilizing the concept of importance sampling, these calculations can be carried out in an arbitrarily large quantum Hilbert space, while still avoidingmore » any approximations that would introduce systematic errors. The only errors are statistical in nature, and as such, their magnitudes are accurately estimated during the course of a simulation. Frustrated spin systems present a major challenge to the QMC method, nevertheless, in many instances progress can be made. In this chapter, the field of magnetic molecules is introduced, paying particular attention to the characteristics that distinguish magnetic molecules from other systems that are studied in condensed matter physics. We briefly outline the typical path by which we learn about magnetic molecules, which requires a close relationship between experiments and theoretical calculations. The typical experiments are introduced here, while the theoretical methods are discussed in the next chapter. Each of these theoretical methods has a considerable limitation, also described in Chapter 2, which together serve to motivate the present work. As is shown throughout the later chapters, the present QMC method is often able to provide useful information where other methods fail. In Chapter 3, the use of Monte Carlo methods in statistical physics is reviewed, building up the fundamental ideas that are necessary in order to understand the method that has been used in this work. With

Does patient reporting lead to earlier detection of drug safety signals? A retrospective comparison of time to reporting between patients and healthcare professionals in a global database.

PubMed

Rolfes, Leàn; van Hunsel, Florence; Caster, Ola; Taavola, Henric; Taxis, Katja; van Puijenbroek, Eugène

2018-03-09

To explore if there is a difference between patients and healthcare professionals (HCPs) in time to reporting drug-adverse drug reaction (ADR) associations that led to drug safety signals. This was a retrospective comparison of time to reporting selected drug-ADR associations which led to drug safety signals between patients and HCPs. ADR reports were selected from the World Health Organization Global database of individual case safety reports, VigiBase. Reports were selected based on drug-ADR associations of actual drug safety signals. Primary outcome was the difference in time to reporting between patients and HCPs. The date of the first report for each individual signal was used as time zero. The difference in time between the date of the reports and time zero was calculated. Statistical differences in timing were analysed on the corresponding survival curves using a Mann-Whitney U test. In total, 2822 reports were included, of which 52.7% were patient reports, with a median of 25% for all included signals. For all signals, median time to signal detection was 10.4 years. Overall, HCPs reported earlier than patients: median 7.0 vs. 8.3 years (P < 0.001). Patients contributed a large proportion of reports on drug-ADR pairs that eventually became signals. HCPs reported 1.3 year earlier than patients. These findings strengthen the evidence on the value of patient reporting in signal detection and highlight an opportunity to encourage patients to report suspected ADRs even earlier in the future. © 2018 The Authors. British Journal of Clinical Pharmacology published by John Wiley & Sons Ltd on behalf of British Pharmacological Society.

Density functional calculations of the Mössbauer parameters in hexagonal ferrite SrFe12O19

NASA Astrophysics Data System (ADS)

Ikeno, Hidekazu

2018-03-01

Mössbauer parameters in a magnetoplumbite-type hexagonal ferrite, SrFe12O19, are computed using the all-electron band structure calculation based on the density functional theory. The theoretical isomer shift and quadrupole splitting are consistent with experimentally obtained values. The absolute values of hyperfine splitting parameters are found to be underestimated, but the relative scale can be reproduced. The present results validate the site-dependence of Mössbauer parameters obtained by analyzing experimental spectra of hexagonal ferrites. The results also show the usefulness of theoretical calculations for increasing the reliability of interpretation of the Mössbauer spectra.

Comparative theoretical and experimental study on novel tri-quinoline system and its anticancer studies

NASA Astrophysics Data System (ADS)

Gayathri, Kasirajan; Radhika, Ramachandran; Shankar, Ramasamy; Malathi, Mahalingam; Savithiri, Krishnaswamy; Sparkes, Hazel A.; Howard, Judith A. K.; Mohan, Palathurai Subramaniam

2017-04-01

A novel compound 2-chloro-3,6-bis-(quinolin-8-yloxymethyl)-quinoline 3 bearing a tri-quinoline moiety has been synthesized from 2-chloro-3,6-dimethyl quinoline 1 and 8-hydroxy quinoline 2 using dry acetone and K2CO3 as a base. 3 has been characterized by using FT-IR, FT-Raman, UV-Vis, 1H NMR, 13C NMR spectra and single crystal X-ray diffraction methods. We have also made a combined experimental and theoretical study on the molecular structure, vibrational spectra, NMR, FT-IR, FT-Raman and UV-Vis spectra of 2-chloro-3,6-bis-(quinolin-8-yloxymethyl)-quinoline. The theoretical studies of the title compound have been evaluated by using density functional theory calculations using B3LYP/6-31+G(d,p) and M06-2X/6-31+G(d,p) level of theories. The calculated theoretical values were found to be in good agreement with the experimental findings. The single crystal structure 3 crystallized in the orthorhombic space group Pna21. The compound 3 exhibits higher cytotoxicity in human cervical cancer cell lines (HeLa) than human breast cancer cell lines (MCF7).

Experimental (FT-IR, FT-Raman, 1H, 13C NMR) and theoretical study of alkali metal 2-aminobenzoates

NASA Astrophysics Data System (ADS)

Samsonowicz, M.; Świsłocka, R.; Regulska, E.; Lewandowski, W.

2008-09-01

The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 2-aminobenzoic acid was studied by the methods of molecular spectroscopy. The vibrational (FT-IR, FT-Raman) and NMR ( 1H and 13C) spectra for 2-aminobenzoic acid and its alkali metal salts were recorded. The assignment of vibrational spectra was done on the basis of literature data, theoretical calculations and our previous experience. Characteristic shifts of bands and changes in intensities of bands along the metal series were observed. The changes of chemical shifts of protons ( 1H NMR) and carbons ( 13C NMR) in the series of studied alkali metal 2-aminobenzoates were observed too. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G ∗∗ basis set. Geometric aromaticity indices, dipole moments and energies were also calculated. The theoretical wavenumbers and intensities of IR and Raman spectra were obtained. The calculated parameters were compared to experimental characteristic of studied compounds.

Multi-configuration Dirac-Hartree-Fock (MCDHF) calculations for Ni XXV

NASA Astrophysics Data System (ADS)

Singh, Narendra; Aggarwal, Sunny

2018-03-01

We present accurate 165 fine-structure energy levels related to the configurations 1s22s2, 1s22p2, 1s2nƖn‧l‧ (n = 2, n‧ = 2, 3, 4, 5, Ɩ = s,p Ɩ‧ = s, p, d, f, g) of Ni XXV which may be useful ion for astrophysical and fusion plasma. For the calculations of energy levels and radiative rates, we have used the multiconfiguration Dirac-Hartree-Fock (MCDHF) method employed in GRASP2K code. The calculations are carried out in the active space approximation with the inclusion of the Breit interaction, the finite nuclear size effect, and quantum electrodynamic corrections. The transition wavelengths, transition probabilities, line strengths, and absorption oscillator strengths are reported for electric dipole (E1), electric quadrupole (E2), magnetic dipole (M1), magnetic quadrupole (M2) transitions from the ground state. We have compared our calculated results with available theoretical and experimental data and good agreement is achieved. We predict new energy levels, oscillator strengths, line strengths and transition probabilities, where no other experimental or theoretical results are available. The present complete set of results should be of great help in line identification and the interpretation of spectra, as well as in the modelling and diagnostics of astrophysical and fusion plasmas.

Calculated Coupling Efficiency Between an Elliptical-Core Optical Fiber and a Silicon Oxynitride Rib Waveguide [Corrected Copy

NASA Technical Reports Server (NTRS)

Tuma, Margaret L.; Beheim, Glenn

1995-01-01

The effective-index method and Marcatili's technique were utilized independently to calculate the electric field profile of a rib channel waveguide. Using the electric field profile calculated from each method, the theoretical coupling efficiency between a single-mode optical fiber and a rib waveguide was calculated using the overlap integral. Perfect alignment was assumed and the coupling efficiency calculated. The coupling efficiency calculation was then repeated for a range of transverse offsets.

A Combined Theoretical and Experimental Study for Silver Electroplating

PubMed Central

Liu, Anmin; Ren, Xuefeng; An, Maozhong; Zhang, Jinqiu; Yang, Peixia; Wang, Bo; Zhu, Yongming; Wang, Chong

2014-01-01

A novel method combined theoretical and experimental study for environmental friendly silver electroplating was introduced. Quantum chemical calculations and molecular dynamic (MD) simulations were employed for predicting the behaviour and function of the complexing agents. Electronic properties, orbital information, and single point energies of the 5,5-dimethylhydantoin (DMH), nicotinic acid (NA), as well as their silver(I)-complexes were provided by quantum chemical calculations based on density functional theory (DFT). Adsorption behaviors of the agents on copper and silver surfaces were investigated using MD simulations. Basing on the data of quantum chemical calculations and MD simulations, we believed that DMH and NA could be the promising complexing agents for silver electroplating. The experimental results, including of electrochemical measurement and silver electroplating, further confirmed the above prediction. This efficient and versatile method thus opens a new window to study or design complexing agents for generalized metal electroplating and will vigorously promote the level of this research region. PMID:24452389

A theoretical study on the characteristics of the intermolecular interactions in the active site of human androsterone sulphotransferase: DFT calculations of NQR and NMR parameters and QTAIM analysis.

PubMed

Astani, Elahe K; Heshmati, Emran; Chen, Chun-Jung; Hadipour, Nasser L

2016-07-01

A theoretical study at the level of density functional theory (DFT) was performed to characterize noncovalent intermolecular interactions, especially hydrogen bond interactions, in the active site of enzyme human androsterone sulphotransferase (SULT2A1/ADT). Geometry optimization, interaction energy, (2)H, (14)N, and (17)O electric field gradient (EFG) tensors, (1)H, (13)C, (17)O, and (15)N chemical shielding (CS) tensors, Natural Bonding Orbital (NBO) analysis, and quantum theory of atoms in molecules (QTAIM) analysis of this active site were investigated. It was found that androsterone (ADT) is able to form hydrogen bonds with residues Ser80, Ile82, and His99 of the active site. The interaction energy calculations and NBO analysis revealed that the ADT molecule forms the strongest hydrogen bond with Ser80. Results revealed that ADT interacts with the other residues through electrostatic and Van der Waals interactions. Results showed that these hydrogen bonds influence on the calculated (2)H, (14)N, and (17)O quadrupole coupling constants (QCCs), as well as (1)H, (13)C, (17)O, and (15)N CS tensors. The magnitude of the QCC and CS changes at each nucleus depends directly on its amount of contribution to the hydrogen bond interaction. Copyright © 2016 Elsevier Inc. All rights reserved.

Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes

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

Nozirov, Farhod, E-mail: teobaldk@gmail.com, E-mail: farhod.nozirov@gmail.com; Stachów, Michał, E-mail: michal.stachow@gmail.com; Kupka, Teobald, E-mail: teobaldk@gmail.com, E-mail: farhod.nozirov@gmail.com

2014-04-14

A theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis- and trans-1,2-difluoroethylenes is reported. The results obtained using density functional theory (DFT) combined with large basis sets and gauge-independent atomic orbital calculations were critically compared with experiment and conventional, higher level correlated electronic structure methods. Accurate structural, vibrational, and NMR parameters of difluoroethylenes were obtained using several density functionals combined with dedicated basis sets. B3LYP/6-311++G(3df,2pd) optimized structures of difluoroethylenes closely reproduced experimental geometries and earlier reported benchmark coupled cluster results, while BLYP/6-311++G(3df,2pd) produced accurate harmonic vibrational frequencies. The most accurate vibrations were obtained using B3LYP/6-311++G(3df,2pd)more » with correction for anharmonicity. Becke half and half (BHandH) density functional predicted more accurate {sup 19}F isotropic shieldings and van Voorhis and Scuseria's τ-dependent gradient-corrected correlation functional yielded better carbon shieldings than B3LYP. A surprisingly good performance of Hartree-Fock (HF) method in predicting nuclear shieldings in these molecules was observed. Inclusion of zero-point vibrational correction markedly improved agreement with experiment for nuclear shieldings calculated by HF, MP2, CCSD, and CCSD(T) methods but worsened the DFT results. The threefold improvement in accuracy when predicting {sup 2}J(FF) in 1,1-difluoroethylene for BHandH density functional compared to B3LYP was observed (the deviations from experiment were −46 vs. −115 Hz)« less

Optimised Iteration in Coupled Monte Carlo - Thermal-Hydraulics Calculations

NASA Astrophysics Data System (ADS)

Hoogenboom, J. Eduard; Dufek, Jan

2014-06-01

This paper describes an optimised iteration scheme for the number of neutron histories and the relaxation factor in successive iterations of coupled Monte Carlo and thermal-hydraulic reactor calculations based on the stochastic iteration method. The scheme results in an increasing number of neutron histories for the Monte Carlo calculation in successive iteration steps and a decreasing relaxation factor for the spatial power distribution to be used as input to the thermal-hydraulics calculation. The theoretical basis is discussed in detail and practical consequences of the scheme are shown, among which a nearly linear increase per iteration of the number of cycles in the Monte Carlo calculation. The scheme is demonstrated for a full PWR type fuel assembly. Results are shown for the axial power distribution during several iteration steps. A few alternative iteration method are also tested and it is concluded that the presented iteration method is near optimal.

Theoretical Sum Frequency Generation Spectroscopy of Peptides

PubMed Central

2015-01-01

Vibrational sum frequency generation (SFG) has become a very promising technique for the study of proteins at interfaces, and it has been applied to important systems such as anti-microbial peptides, ion channel proteins, and human islet amyloid polypeptide. Moreover, so-called “chiral” SFG techniques, which rely on polarization combinations that generate strong signals primarily for chiral molecules, have proven to be particularly discriminatory of protein secondary structure. In this work, we present a theoretical strategy for calculating protein amide I SFG spectra by combining line-shape theory with molecular dynamics simulations. We then apply this method to three model peptides, demonstrating the existence of a significant chiral SFG signal for peptides with chiral centers, and providing a framework for interpreting the results on the basis of the dependence of the SFG signal on the peptide orientation. We also examine the importance of dynamical and coupling effects. Finally, we suggest a simple method for determining a chromophore’s orientation relative to the surface using ratios of experimental heterodyne-detected signals with different polarizations, and test this method using theoretical spectra. PMID:25203677

Standard model with a complex scalar singlet: Cosmological implications and theoretical considerations

NASA Astrophysics Data System (ADS)

Chiang, Cheng-Wei; Ramsey-Musolf, Michael J.; Senaha, Eibun

2018-01-01

We analyze the theoretical and phenomenological considerations for the electroweak phase transition and dark matter in an extension of the standard model with a complex scalar singlet (cxSM). In contrast with earlier studies, we use a renormalization group improved scalar potential and treat its thermal history in a gauge-invariant manner. We find that the parameter space consistent with a strong first-order electroweak phase transition (SFOEWPT) and present dark matter phenomenological constraints is significantly restricted compared to results of a conventional, gauge-noninvariant analysis. In the simplest variant of the cxSM, recent LUX data and a SFOEWPT require a dark matter mass close to half the mass of the standard model-like Higgs boson. We also comment on various caveats regarding the perturbative treatment of the phase transition dynamics.

Development of Theoretical and Numerical Techniques for Achieving Stability in Gyrotron Traveling-Wave Amplifiers.

DTIC Science & Technology

1989-02-01

analysis methods diverge significantly. The electron current density found in Eq. 2.106 may be evaluated" as I J ...S..Y.v Yvt r t) (2.107) 0 ZO where 10...will be specified by the geometry and mode under consider- ation. It was noted earlier that the point of divergence between the two principle...techniques lies in the methods used to calculate the current density. Actually, the divergence is present only in theory. Theoreti- cally and numerically, Eq

Theoretical Limits on Multiuser Molecular Communication in Internet of Nano-Bio Things.

PubMed

Dinc, Ergin; Akan, Ozgur B

2017-06-01

In nano-bio networks, multiple transmitter-receiver pairs will operate in the same medium. Both inter-symbol interference and multi-user interference can cause saturation at the receiver side, and this effect may cause an outage. Thus, we propose a tractable framework to calculate the theoretical operating points for fully absorbing receiver.

C2 Fragmentation Energy of C60 Revisited: Theory Disagrees with Most Experiments

NASA Technical Reports Server (NTRS)

Boese, A. Daniel; Scuseria, Gustavo E.

1998-01-01

Following our earlier work on the subject, we have carried out density functional theory (DFT) and second-order Moller-Plesset perturbation theory (MP2) calculations of the dissociation energy of the reaction C60 yields C58 + C2 using polarized basis sets and geometries optimized with DFT methods. The present theoretical results support an electronic fragmentation energy D(sub e) around 10-11 eV in disagreement with most experimental results that place the dissociation energy D(sub o) (including zero point energy) around 7-8 eV. The plausible errors remaining in the theoretical calculations are unlikely to account for this big difference (2-4 eV).

Consideration of the Aluminum Distribution in Zeolites in Theoretical and Experimental Catalysis Research

DOE PAGES

Knott, Brandon C.; Nimlos, Claire T.; Robichaud, David J.; ...

2017-12-11

Research efforts in zeolite catalysis have become increasingly cognizant of the diversity in structure and function resulting from the distribution of framework aluminum atoms, through emerging reports of catalytic phenomena that fall outside those recognizable as the shape-selective ones emblematic of its earlier history. Molecular-level descriptions of how active-site distributions affect catalysis are an aspirational goal articulated frequently in experimental and theoretical research, yet they are limited by imprecise knowledge of the structure and behavior of the zeolite materials under interrogation. In experimental research, higher precision can result from more reliable control of structure during synthesis and from more robustmore » and quantitative structural and kinetic characterization probes. In theoretical research, construction of models with specific aluminum locations and distributions seldom capture the heterogeneity inherent to the materials studied by experiment. In this Perspective, we discuss research findings that appropriately frame the challenges in developing more predictive synthesis-structure-function relations for zeolites, highlighting studies on ZSM-5 zeolites that are among the most structurally complex molecular sieve frameworks and the most widely studied because of their versatility in commercial applications. We discuss research directions to address these challenges and forge stronger connections between zeolite structure, composition, and active sites to catalytic function. Such connections promise to aid in bridging the findings of theoretical and experimental catalysis research, and transforming zeolite active site design from an empirical endeavor into a more predictable science founded on validated models.« less

Consideration of the Aluminum Distribution in Zeolites in Theoretical and Experimental Catalysis Research

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

Knott, Brandon C.; Nimlos, Claire T.; Robichaud, David J.

Research efforts in zeolite catalysis have become increasingly cognizant of the diversity in structure and function resulting from the distribution of framework aluminum atoms, through emerging reports of catalytic phenomena that fall outside those recognizable as the shape-selective ones emblematic of its earlier history. Molecular-level descriptions of how active-site distributions affect catalysis are an aspirational goal articulated frequently in experimental and theoretical research, yet they are limited by imprecise knowledge of the structure and behavior of the zeolite materials under interrogation. In experimental research, higher precision can result from more reliable control of structure during synthesis and from more robustmore » and quantitative structural and kinetic characterization probes. In theoretical research, construction of models with specific aluminum locations and distributions seldom capture the heterogeneity inherent to the materials studied by experiment. In this Perspective, we discuss research findings that appropriately frame the challenges in developing more predictive synthesis-structure-function relations for zeolites, highlighting studies on ZSM-5 zeolites that are among the most structurally complex molecular sieve frameworks and the most widely studied because of their versatility in commercial applications. We discuss research directions to address these challenges and forge stronger connections between zeolite structure, composition, and active sites to catalytic function. Such connections promise to aid in bridging the findings of theoretical and experimental catalysis research, and transforming zeolite active site design from an empirical endeavor into a more predictable science founded on validated models.« less

Theoretically Founded Optimization of Auctioneer's Revenues in Expanding Auctions

NASA Astrophysics Data System (ADS)

Rabin, Jonathan; Shehory, Onn

The expanding auction is a multi-unit auction which provides the auctioneer with control over the outcome of the auction by means of dynamically adding items for sale. Previous research on the expanding auction has provided a numeric method to calculate a strategy that optimizes the auctioneer's revenue. In this paper, we analyze various theoretical properties of the expanding auction, and compare it to VCG, a multi-unit auction protocol known in the art. We examine the effects of errors in the auctioneer's estimation of the buyers' maximal bidding values and prove a theoretical bound on the ratio between the revenue yielded by the Informed Decision Strategy (IDS) and the post-optimal strategy. We also analyze the relationship between the auction step and the optimal revenue and introduce a method of computing this optimizing step. We further compare the revenues yielded by the use of IDS with an expanding auction to those of the VCG mechanism and determine the conditions under which the former outperforms the latter. Our work provides new insight into the properties of the expanding auction. It further provides theoretically founded means for optimizing the revenue of auctioneer.

Electronic Structure Calculation of Permanent Magnets using the KKR Green's Function Method

NASA Astrophysics Data System (ADS)

Doi, Shotaro; Akai, Hisazumi

2014-03-01

Electronic structure and magnetic properties of permanent magnetic materials, especially Nd2Fe14B, are investigated theoretically using the KKR Green's function method. Important physical quantities in magnetism, such as magnetic moment, Curie temperature, and anisotropy constant, which are obtained from electronics structure calculations in both cases of atomic-sphere-approximation and full-potential treatment, are compared with past band structure calculations and experiments. The site preference of heavy rare-earth impurities are also evaluated through the calculation of formation energy with the use of coherent potential approximations. Further, the development of electronic structure calculation code using the screened KKR for large super-cells, which is aimed at studying the electronic structure of realistic microstructures (e.g. grain boundary phase), is introduced with some test calculations.

Theoretical and Experimental Photoelectron Spectroscopy Characterization of the Ground State of Thymine Cation.

PubMed

Majdi, Youssef; Hochlaf, Majdi; Pan, Yi; Lau, Kai-Chung; Poisson, Lionel; Garcia, Gustavo A; Nahon, Laurent; Al-Mogren, Muneerah Mogren; Schwell, Martin

2015-06-11

We report on the vibronic structure of the ground state X̃(2)A″ of the thymine cation, which has been measured using a threshold photoelectron photoion coincidence technique and vacuum ultraviolet synchrotron radiation. The threshold photoelectron spectrum, recorded over ∼0.7 eV above the ionization potential (i.e., covering the whole ground state of the cation) shows rich vibrational structure that has been assigned with the help of calculated anharmonic modes of the ground electronic cation state at the PBE0/aug-cc-pVDZ level of theory. The adiabatic ionization energy has been experimentally determined as AIE = 8.913 ± 0.005 eV, in very good agreement with previous high resolution results. The corresponding theoretical value of AIE = 8.917 eV has been calculated in this work with the explicitly correlated method/basis set (R)CCSD(T)-F12/cc-pVTZ-F12, which validates the theoretical approach and benchmarks its accuracy for future studies of medium-sized biological molecules.

Theoretical study of the properties of X-ray diffraction moiré fringes. I

PubMed Central

Yoshimura, Jun-ichi

2015-01-01

A detailed and comprehensive theoretical description of X-ray diffraction moiré fringes for a bicrystal specimen is given on the basis of a calculation by plane-wave dynamical diffraction theory. Firstly, prior to discussing the main subject of the paper, a previous article [Yoshimura (1997 ▸). Acta Cryst. A53, 810–812] on the two-dimensionality of diffraction moiré patterns is restated on a thorough calculation of the moiré interference phase. Then, the properties of moiré fringes derived from the above theory are explained for the case of a plane-wave diffraction image, where the significant effect of Pendellösung intensity oscillation on the moiré pattern when the crystal is strained is described in detail with theoretically simulated moiré images. Although such plane-wave moiré images are not widely observed in a nearly pure form, knowledge of their properties is essential for the understanding of diffraction moiré fringes in general. PMID:25970298

Calculation of broadband time histories of ground motion, Part II: Kinematic and dynamic modeling using theoretical Green's functions and comparison with the 1994 northridge earthquake

USGS Publications Warehouse

Hartzell, S.; Guatteri, Mariagiovanna; Mai, P.M.; Liu, P.-C.; Fisk, M. R.

2005-01-01

In the evolution of methods for calculating synthetic time histories of ground motion for postulated earthquakes, kinematic source models have dominated to date because of their ease of application. Dynamic models, however, which incorporate a physical relationship between important faulting parameters of stress drop, slip, rupture velocity, and rise time, are becoming more accessible. This article compares a class of kinematic models based on the summation of a fractal distribution of subevent sizes with a dynamic model based on the slip-weakening friction law. Kinematic modeling is done for the frequency band 0.2 to 10.0. Hz, dynamic models are calculated from 0.2 to 2.0. Hz. The strong motion data set for the 1994 Northridge earthquake is used to evaluate and compare the synthetic time histories. Source models are propagated to the far field by convolution with 1D and 3D theoretical Green’s functions. In addition, the kinematic model is used to evaluate the importance of propagation path effects: velocity structure, scattering, and nonlinearity. At present, the kinematic model gives a better broadband fit to the Northridge ground motion than the simple slip-weakening dynamic model. In general, the dynamic model overpredicts rise times and produces insufficient shorter-period energy. Within the context of the slip-weakening model, the Northridge ground motion requires a short slip-weakening distance, on the order of 0.15 m or less. A more complex dynamic model including rate weakening or one that allows shorter rise times near the hypocenter may fit the data better.

Quantum chemistry calculation of resveratrol and related stilbenes

NASA Astrophysics Data System (ADS)

Del Nero, J.; de Melo, C. P.

2003-01-01

We report a semiempirical investigation of the first excited states and of the spectroscopic properties of resveratrol, a phytoalexin with well-known antioxidative properties, and of structurally related stilbenes. The analysis of the calculated bond length and charge rearrangements resulting from the photoexcitation and of the corresponding theoretical spectra gives us some insight of how chemical modifications of these molecules could affect the possible physiological properties of resveratrol.

Calculation of solar wind flows about terrestrial planets

NASA Technical Reports Server (NTRS)

Stahara, S. S.; Spreiter, J. R.

1982-01-01

A computational model was developed for the determination of the plasma and magnetic field properties of the global interaction of the solar wind with terrestrial planetary magneto/ionospheres. The theoretical method is based on an established single fluid, steady, dissipationless, magnetohydrodynamic continuum model, and is appropriate for the calculation of supersonic, super Alfvenic solar wind flow past terrestrial planets. A summary is provided of the important research results.

Incidence, prevalence, and hybrid approaches to calculating disability-adjusted life years

PubMed Central

2012-01-01

When disability-adjusted life years are used to measure the burden of disease on a population in a time interval, they can be calculated in several different ways: from an incidence, pure prevalence, or hybrid perspective. I show that these calculation methods are not equivalent and discuss some of the formal difficulties each method faces. I show that if we don’t discount the value of future health, there is a sense in which the choice of calculation method is a mere question of accounting. Such questions can be important, but they don’t raise deep theoretical concerns. If we do discount, however, choice of calculation method can change the relative burden attributed to different conditions over time. I conclude by recommending that studies involving disability-adjusted life years be explicit in noting what calculation method is being employed and in explaining why that calculation method has been chosen. PMID:22967055

Synthesis, crystal structure, biological activity and theoretical calculations of novel isoxazole derivatives

NASA Astrophysics Data System (ADS)

Jin, R. Y.; Sun, X. H.; Liu, Y. F.; Long, W.; Chen, B.; Shen, S. Q.; Ma, H. X.

2016-01-01

Series of isoxazole derivatives were synthesized by substituted chalcones and 2-chloro-6-fluorobenzene formaldehyde oxime with 1,3-dipolar cycloaddition. The target compounds were determined by melting point, IR, 1H NMR, elemental analyses and HRMS. The crystal structure of compound 3a was detected by X-ray diffraction and it crystallizes in the triclinic space group p2(1)/c with z = 4. The molecular geometry of compound 3a was optimized using density functional theory (DFT/B3LYP) method with the 6-31G+(d,p) basis set in the ground state. From the optimized geometry of the molecule, FT-IR, FT-Raman, HOMO-LUMO and natural bond orbital (NBO) were calculated at B3LYP/6-31G+(d,p) level. Finally, the antifungal activity of the synthetic compounds were evaluated against Pythium solani, Gibberella nicotiancola, Fusarium oxysporium f.sp. niveum and Gibberella saubinetii.

Aerodynamic design and analysis system for supersonic aircraft. Part 1: General description and theoretical development

NASA Technical Reports Server (NTRS)

Middleton, W. D.; Lundry, J. L.

1975-01-01

An integrated system of computer programs has been developed for the design and analysis of supersonic configurations. The system uses linearized theory methods for the calculation of surface pressures and supersonic area rule concepts in combination with linearized theory for calculation of aerodynamic force coefficients. Interactive graphics are optional at the user's request. This part presents a general description of the system and describes the theoretical methods used.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Changing facial phenotype in Cohen syndrome: towards clues for an earlier diagnosis.

PubMed

El Chehadeh-Djebbar, Salima; Blair, Edward; Holder-Espinasse, Muriel; Moncla, Anne; Frances, Anne-Marie; Rio, Marlène; Debray, François-Guillaume; Rump, Patrick; Masurel-Paulet, Alice; Gigot, Nadège; Callier, Patrick; Duplomb, Laurence; Aral, Bernard; Huet, Frédéric; Thauvin-Robinet, Christel; Faivre, Laurence

2013-07-01

Cohen syndrome (CS) is a rare autosomal recessive condition caused by mutations and/or large rearrangements in the VPS13B gene. CS clinical features, including developmental delay, the typical facial gestalt, chorioretinal dystrophy (CRD) and neutropenia, are well described. CS diagnosis is generally raised after school age, when visual disturbances lead to CRD diagnosis and to VPS13B gene testing. This relatively late diagnosis precludes accurate genetic counselling. The aim of this study was to analyse the evolution of CS facial features in the early period of life, particularly before school age (6 years), to find clues for an earlier diagnosis. Photographs of 17 patients with molecularly confirmed CS were analysed, from birth to preschool age. By comparing their facial phenotype when growing, we show that there are no special facial characteristics before 1 year. However, between 2 and 6 years, CS children already share common facial features such as a short neck, a square face with micrognathia and full cheeks, a hypotonic facial appearance, epicanthic folds, long ears with an everted upper part of the auricle and/or a prominent lobe, a relatively short philtrum, a small and open mouth with downturned corners, a thick lower lip and abnormal eye shapes. These early transient facial features evolve to typical CS facial features with aging. These observations emphasize the importance of ophthalmological tests and neutrophil count in children in preschool age presenting with developmental delay, hypotonia and the facial features we described here, for an earlier CS diagnosis.

Identified research directions for using manufacturing knowledge earlier in the product lifecycle

PubMed Central

Hedberg, Thomas D.; Hartman, Nathan W.; Rosche, Phil; Fischer, Kevin

2016-01-01

Design for Manufacturing (DFM), especially the use of manufacturing knowledge to support design decisions, has received attention in the academic domain. However, industry practice has not been studied enough to provide solutions that are mature for industry. The current state of the art for DFM is often rule-based functionality within Computer-Aided Design (CAD) systems that enforce specific design requirements. That rule-based functionality may or may not dynamically affect geometry definition. And, if rule-based functionality exists in the CAD system, it is typically a customization on a case-by-case basis. Manufacturing knowledge is a phrase with vast meanings, which may include knowledge on the effects of material properties decisions, machine and process capabilities, or understanding the unintended consequences of design decisions on manufacturing. One of the DFM questions to answer is how can manufacturing knowledge, depending on its definition, be used earlier in the product lifecycle to enable a more collaborative development environment? This paper will discuss the results of a workshop on manufacturing knowledge that highlights several research questions needing more study. This paper proposes recommendations for investigating the relationship of manufacturing knowledge with shape, behavior, and context characteristics of product to produce a better understanding of what knowledge is most important. In addition, the proposal includes recommendations for investigating the system-level barriers to reusing manufacturing knowledge and how model-based manufacturing may ease the burden of knowledge sharing. Lastly, the proposal addresses the direction of future research for holistic solutions of using manufacturing knowledge earlier in the product lifecycle. PMID:27990027

Identified research directions for using manufacturing knowledge earlier in the product lifecycle.

PubMed

Hedberg, Thomas D; Hartman, Nathan W; Rosche, Phil; Fischer, Kevin

2017-01-01

Design for Manufacturing (DFM), especially the use of manufacturing knowledge to support design decisions, has received attention in the academic domain. However, industry practice has not been studied enough to provide solutions that are mature for industry. The current state of the art for DFM is often rule-based functionality within Computer-Aided Design (CAD) systems that enforce specific design requirements. That rule-based functionality may or may not dynamically affect geometry definition. And, if rule-based functionality exists in the CAD system, it is typically a customization on a case-by-case basis. Manufacturing knowledge is a phrase with vast meanings, which may include knowledge on the effects of material properties decisions, machine and process capabilities, or understanding the unintended consequences of design decisions on manufacturing. One of the DFM questions to answer is how can manufacturing knowledge, depending on its definition, be used earlier in the product lifecycle to enable a more collaborative development environment? This paper will discuss the results of a workshop on manufacturing knowledge that highlights several research questions needing more study. This paper proposes recommendations for investigating the relationship of manufacturing knowledge with shape, behavior, and context characteristics of product to produce a better understanding of what knowledge is most important. In addition, the proposal includes recommendations for investigating the system-level barriers to reusing manufacturing knowledge and how model-based manufacturing may ease the burden of knowledge sharing. Lastly, the proposal addresses the direction of future research for holistic solutions of using manufacturing knowledge earlier in the product lifecycle.

Inevitable end-of-21st-century trends toward earlier surface runoff timing in California's Sierra Nevada Mountains

NASA Astrophysics Data System (ADS)

Schwartz, M. A.; Hall, A. D.; Sun, F.; Walton, D.; Berg, N.

2015-12-01

Hybrid dynamical-statistical downscaling is used to produce surface runoff timing projections for California's Sierra Nevada, a high-elevation mountain range with significant seasonal snow cover. First, future climate change projections (RCP8.5 forcing scenario, 2081-2100 period) from five CMIP5 global climate models (GCMs) are dynamically downscaled. These projections reveal that future warming leads to a shift toward earlier snowmelt and surface runoff timing throughout the Sierra Nevada region. Relationships between warming and surface runoff timing from the dynamical simulations are used to build a simple statistical model that mimics the dynamical model's projected surface runoff timing changes given GCM input or other statistically-downscaled input. This statistical model can be used to produce surface runoff timing projections for other GCMs, periods, and forcing scenarios to quantify ensemble-mean changes, uncertainty due to intermodel variability and consequences stemming from choice of forcing scenario. For all CMIP5 GCMs and forcing scenarios, significant trends toward earlier surface runoff timing occur at elevations below 2500m. Thus, we conclude that trends toward earlier surface runoff timing by the end-of-the-21st century are inevitable. The changes to surface runoff timing diagnosed in this study have implications for many dimensions of climate change, including impacts on surface hydrology, water resources, and ecosystems.

Theoretical analysis of the transition-state spectrum of the cyclooctatetraene unimolecular reaction: Three degree-of-freedom model calculations

NASA Astrophysics Data System (ADS)

Yoshida, Takahiko; Tokizaki, Chihiro; Takayanagi, Toshiyuki

2015-08-01

A three degree-of-freedom potential energy surface of the cyclooctatetraene (COT) unimolecular reaction that can describe both ring-inversion (D2d ↔ D2d) and double bond-alternation (D4h ↔ D4h) processes was constructed using complete active space self-consistent field calculations. The potential energy surface was used to simulate the experimentally measured transition-state spectrum by calculating the photodetachment spectrum of the COT anion with time-dependent wave packet formalism. The calculated spectrum reproduces the experimental result well. We also analyzed wavefunction properties at spectral peak positions to understand the COT unimolecular reaction dynamics.

Theoretical studies of surface enhanced hyper-Raman spectroscopy: The chemical enhancement mechanism

NASA Astrophysics Data System (ADS)

Valley, Nicholas; Jensen, Lasse; Autschbach, Jochen; Schatz, George C.

2010-08-01

Hyper-Raman spectra for pyridine and pyridine on the surface of a tetrahedral 20 silver atom cluster are calculated using static hyperpolarizability derivatives obtained from time dependent density functional theory. The stability of the results with respect to choice of exchange-correlation functional and basis set is verified by comparison with experiment and with Raman spectra calculated for the same systems using the same methods. Calculated Raman spectra were found to match well with experiment and previous theoretical calculations. The calculated normal and surface enhanced hyper-Raman spectra closely match experimental results. The chemical enhancement factors for hyper-Raman are generally larger than for Raman (102-104 versus 101-102). Integrated hyper-Raman chemical enhancement factors are presented for a set of substituted pyridines. A two-state model is developed to predict these chemical enhancement factors and this was found to work well for the majority of the molecules considered, providing a rationalization for the difference between hyper-Raman and Raman enhancement factors.

Progress toward time-resolved molecular imaging: A theoretical study of optimal parameters in static photoelectron holography

NASA Astrophysics Data System (ADS)

Sun, S. X.-L.; Kaduwela, A. P.; Gray, A. X.; Fadley, C. S.

2014-05-01

The availability of short-pulse free-electron lasers has led to the idea of using photoelectron holography as a method of directly imaging molecular dissociations or reactions in real time, as, e.g., in a recent theoretical study by Krasniqi et al., [F. Krasniqi, B. Najjari, L. Strüder, D. Rolles, A. Voitkiv, and J. Ullrich, Phys. Rev. A 81, 033411 (2010), 10.1103/PhysRevA.81.033411]. In this paper, we extend this earlier work and in particular look at two critical questions concerning the optimum type of data required for such holographic imaging: the choice of photoelectron kinetic energy (e.g., ˜300 eV versus ˜1700 eV as in the prior study), and the use of a single energy or multiple energies. After verifying that our calculations fully duplicate those in this prior paper, we show that using lower energies is preferable to using higher energies for image quality, a conclusion consistent with prior photoelectron holography studies at surfaces, and that multiple lower energies in which the hologram effectively spans a volume in kspace yields the best quality images that should be useful for such "molecular movies." Although the amount of data required for such multi-energy holography is roughly an order of magnitude higher than that for single energy, the reduction of artifacts and the improved quality of the images suggest this as the optimum ultimate future strategy for such dynamic imaging.

FORTRAN 4 computer program for calculation of thermodynamic and transport properties of complex chemical systems

NASA Technical Reports Server (NTRS)

Svehla, R. A.; Mcbride, B. J.

1973-01-01

A FORTRAN IV computer program for the calculation of the thermodynamic and transport properties of complex mixtures is described. The program has the capability of performing calculations such as:(1) chemical equilibrium for assigned thermodynamic states, (2) theoretical rocket performance for both equilibrium and frozen compositions during expansion, (3) incident and reflected shock properties, and (4) Chapman-Jouguet detonation properties. Condensed species, as well as gaseous species, are considered in the thermodynamic calculation; but only the gaseous species are considered in the transport calculations.

Theoretical studies of photoexcitation and ionization in H2O

NASA Technical Reports Server (NTRS)

Diercksen, G. H. F.; Kraemer, W. P.; Rescigno, T. N.; Bender, C. F.; Mckoy, B. V.; Langhoff, S. R.; Langhoff, P. W.

1982-01-01

Theoretical studies using Franck-Condon and static-exchange approximations are reported for the complete dipole excitation and ionization spectrum in H2O, where (1) large Cartesian Gaussian basis sets are used to represent the required discrete and continuum electronic eigenfunctions at the ground state equilibrium geometry, and (2) previously devised moment-theory techniques are employed in constructing the continuum oscillator-strength densities from the calculated spectra. Comparisons are made of the calculated excitation and ionization profiles with recent experimental photoabsorption studies and corresponding spectral assignments, electron impact-excitation cross sections, and dipole and synchrotron-radiation studies of partial-channel photoionization cross sections. The calculated partial-channel cross sections are found to be atomic-like, and dominated by 2p-kd components. It is suggested that the latter transition couples with the underlying 1b(1)-kb(1) channel, accounting for a prominent feature in recent synchrotron-radiation measurements.

Accurate line intensities of methane from first-principles calculations

NASA Astrophysics Data System (ADS)

Nikitin, Andrei V.; Rey, Michael; Tyuterev, Vladimir G.

2017-10-01

In this work, we report first-principle theoretical predictions of methane spectral line intensities that are competitive with (and complementary to) the best laboratory measurements. A detailed comparison with the most accurate data shows that discrepancies in integrated polyad intensities are in the range of 0.4%-2.3%. This corresponds to estimations of the best available accuracy in laboratory Fourier Transform spectra measurements for this quantity. For relatively isolated strong lines the individual intensity deviations are in the same range. A comparison with the most precise laser measurements of the multiplet intensities in the 2ν3 band gives an agreement within the experimental error margins (about 1%). This is achieved for the first time for five-atomic molecules. In the Supplementary Material we provide the lists of theoretical intensities at 269 K for over 5000 strongest transitions in the range below 6166 cm-1. The advantage of the described method is that this offers a possibility to generate fully assigned exhaustive line lists at various temperature conditions. Extensive calculations up to 12,000 cm-1 including high-T predictions will be made freely available through the TheoReTS information system (http://theorets.univ-reims.fr, http://theorets.tsu.ru) that contains ab initio born line lists and provides a user-friendly graphical interface for a fast simulation of the absorption cross-sections and radiance.

Theoretical studies on the inactivation mechanism of γ-aminobutyric acid aminotransferase.

PubMed

Durak, A T; Gökcan, H; Konuklar, F A S

2011-07-21

The inactivation mechanism of γ-aminobutyric acid aminotransferase (GABA-AT) in the presence of γ-vinyl-aminobutyric acid, an anti-epilepsy drug, has been studied by means of theoretical calculations. Density functional theory methods have been applied to compare the three experimentally proposed inactivation mechanisms (Silverman et al., J. Biol. Chem., 2004, 279, 363). All the calculations were performed at the B3LYP/6-31+G(d,p) level of theory. Single point solvent calculations were carried out in water, by means of an integral equation formalism-polarizable continuum model (IEFPCM) at the B3LYP/6-31+G(d,p) level of theory. The present calculations provide an insight into the mechanistic preferences of the inactivation reaction of GABA-AT. The results also allow us to elucidate the key factors behind the mechanistic preferences. The computations also confirm the importance of explicit water molecules around the reacting center in the proton transfer steps.

A theoretical analysis of deformation behavior of auxetic plied yarn structure

NASA Astrophysics Data System (ADS)

Zeng, Jifang; Hu, Hong

2018-07-01

This paper presents a theoretical analysis of the auxetic plied yarn (APY) structure formed with two types of single yarns having different diameter and modulus. A model which can be used to predict its deformation behavior under axial extension is developed based on the theoretical analysis. The developed model is first compared with the experimental data obtained in the previous study, and then used to predict the effects of different structural and material parameters on the auxetic behavior of the APY. The calculation results show that the developed model can correctly predict the variation trend of the auxetic behavior of the APY, which first increases and then decrease with the increase of the axial strain. The calculation results also indicate that the auxetic behavior of the APY simultaneously depends on the diameter ratio of the soft yarn and stiff yarn as well as the ratio between the pitch length and stiff yarn diameter. The study provides a way to design and fabricate APYs with the same auxetic behavior by using different soft and stiff yarns as long as these two ratios are kept unchanged.

Peak clustering in two-dimensional gas chromatography with mass spectrometric detection based on theoretical calculation of two-dimensional peak shapes: the 2DAid approach.

PubMed

van Stee, Leo L P; Brinkman, Udo A Th

2011-10-28

A method is presented to facilitate the non-target analysis of data obtained in temperature-programmed comprehensive two-dimensional (2D) gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-ToF-MS). One main difficulty of GC×GC data analysis is that each peak is usually modulated several times and therefore appears as a series of peaks (or peaklets) in the one-dimensionally recorded data. The proposed method, 2DAid, uses basic chromatographic laws to calculate the theoretical shape of a 2D peak (a cluster of peaklets originating from the same analyte) in order to define the area in which the peaklets of each individual compound can be expected to show up. Based on analyte-identity information obtained by means of mass spectral library searching, the individual peaklets are then combined into a single 2D peak. The method is applied, amongst others, to a complex mixture containing 362 analytes. It is demonstrated that the 2D peak shapes can be accurately predicted and that clustering and further processing can reduce the final peak list to a manageable size. Copyright © 2011 Elsevier B.V. All rights reserved.

Theoretical investigations on structural, elastic and electronic properties of thallium halides

NASA Astrophysics Data System (ADS)

Singh, Rishi Pal; Singh, Rajendra Kumar; Rajagopalan, Mathrubutham

2011-04-01

Theoretical investigations on structural, elastic and electronic properties, viz. ground state lattice parameter, elastic moduli and density of states, of thallium halides (viz. TlCl and TlBr) have been made using the full potential linearized augmented plane wave method within the generalized gradient approximation (GGA). The ground state lattice parameter and bulk modulus and its pressure derivative have been obtained using optimization method. Young's modulus, shear modulus, Poisson ratio, sound velocities for longitudinal and shear waves, Debye average velocity, Debye temperature and Grüneisen parameter have also been calculated for these compounds. Calculated structural, elastic and other parameters are in good agreement with the available data.

Theoretical study of the XP3 (X = Al, B, Ga) clusters

NASA Astrophysics Data System (ADS)

Ueno, Leonardo T.; Lopes, Cinara; Malaspina, Thaciana; Roberto-Neto, Orlando; Canuto, Sylvio; Machado, Francisco B. C.

2012-05-01

The lowest singlet and triplet states of AlP3, GaP3 and BP3 molecules with Cs, C2v and C3v symmetries were characterized using the B3LYP functional and the aug-cc-pVTZ and aug-cc-pVQZ correlated consistent basis sets. Geometrical parameters and vibrational frequencies were calculated and compared to existent experimental and theoretical data. Relative energies were obtained with single point CCSD(T) calculations using the aug-cc-pVTZ, aug-cc-pVQZ and aug-cc-pV5Z basis sets, and then extrapolating to the complete basis set (CBS) limit.

Synthesis of 2-(bis(cyanomethyl)amino)-2-oxoethyl methacrylate monomer molecule and its characterization by experimental and theoretical methods

NASA Astrophysics Data System (ADS)

Sas, E. B.; Cankaya, N.; Kurt, M.

2018-06-01

In this work 2-(bis(cyanomethyl)amino)-2-oxoethyl methacrylate monomer has been synthesized as newly, characterized both experimentally and theoretically. Experimentally, it has been characterized by FT-IR, FT-Raman, 1H and 13C NMR spectroscopy techniques. The theoretical calculations have been performed with Density Functional Theory (DFT) including B3LYP method. The scaled theoretical wavenumbers have been assigned based on total energy distribution (TED). Electronic properties of monomer have been performed using time-dependent TD-DFT/B3LYP/B3LYP/6-311G++(d,p) method. The results of experimental have been compared with theoretical values. Both experimental and theoretical methods have shown that the monomer was suitable for the literature.

TAD- THEORETICAL AERODYNAMICS PROGRAM

NASA Technical Reports Server (NTRS)

Barrowman, J.

1994-01-01

This theoretical aerodynamics program, TAD, was developed to predict the aerodynamic characteristics of vehicles with sounding rocket configurations. These slender, axisymmetric finned vehicle configurations have a wide range of aeronautical applications from rockets to high speed armament. Over a given range of Mach numbers, TAD will compute the normal force coefficient derivative, the center-of-pressure, the roll forcing moment coefficient derivative, the roll damping moment coefficient derivative, and the pitch damping moment coefficient derivative of a sounding rocket configured vehicle. The vehicle may consist of a sharp pointed nose of cone or tangent ogive shape, up to nine other body divisions of conical shoulder, conical boattail, or circular cylinder shape, and fins of trapezoid planform shape with constant cross section and either three or four fins per fin set. The characteristics computed by TAD have been shown to be accurate to within ten percent of experimental data in the supersonic region. The TAD program calculates the characteristics of separate portions of the vehicle, calculates the interference between separate portions of the vehicle, and then combines the results to form a total vehicle solution. Also, TAD can be used to calculate the characteristics of the body or fins separately as an aid in the design process. Input to the TAD program consists of simple descriptions of the body and fin geometries and the Mach range of interest. Output includes the aerodynamic characteristics of the total vehicle, or user-selected portions, at specified points over the mach range. The TAD program is written in FORTRAN IV for batch execution and has been implemented on an IBM 360 computer with a central memory requirement of approximately 123K of 8 bit bytes. The TAD program was originally developed in 1967 and last updated in 1972.

The crystallographic, spectroscopic and theoretical studies on (E)-2-(((4-chlorophenyl)imino)methyl)-5-(diethylamino)phenol and (E)-2-(((3-chlorophenyl)imino)methyl)-5-(diethylamino)phenol molecules

NASA Astrophysics Data System (ADS)

Demirtaş, Güneş; Dege, Necmi; Ağar, Erbil; Uzun, Sümeyye Gümüş

2018-01-01

Two new salicylideneaniline (SA) derivative compounds (E)-2-(((4-chlorophenyl)imino)methyl)-5-(diethylamino)phenol, compound (I), and (E)-2-(((3-chlorophenyl)imino)methyl)-5-(diethylamino)phenol, compound (II), have been synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy, 1H NMR, 13C NMR and theoretical methods. Both of the compounds which are Schiff base derivatives are isomer of each other. While the compound (I) crystallizes in centrosymmetric monoclinic space group P 21/c, the compound (II) crystallizes in orthorhombic space group P 212121. The theoretical parameters of the molecules have been calculated by using Hartree-Fock (HF) and density functional theory (DFT/B3LYP) with 6-31G (d,p) basis set. These theoretical parameters have been compared with the experimental parameters obtained by XRD. The experimental geometries of the compounds have been superimposed with the theoretical geometries calculated by HF and DFT methods. Furthermore, the theoretical IR calculations, molecular electrostatic potential maps (MEP) and frontier molecular orbitals have been created for the compounds.

Projection-operator calculations of the lowest e(-)-He resonance

NASA Technical Reports Server (NTRS)

Berk, A.; Bhatia, A. K.; Junker, B. R.; Temkin, A.

1986-01-01

The 1s (2s)2:2S Schulz resonance of He(-) is investigated theoretically, applying the full projection-operator formalism developed by Temkin and Bhatia (1985) in a Rayleigh-Ritz variational calculation. The technique is described in detail, and results for five different approximations of the He target state are presented in a table. Good convergence is obtained, but it is found that even the best calculated value of the resonance is about 130 meV higher than the experimentally measured value of 19.367 + or - 0.007 eV (Brunt et al., 1977), a discrepancy attributed to the contribution of the shift in the Feshbach formalism.

Dipole moments and solvatochromism of metal complexes: principle photophysical and theoretical approach.

PubMed

Loukova, Galina V; Milov, Alexey A; Vasiliev, Vladimir P; Minkin, Vladimir I

2016-07-21

For metal-based compounds, the ground- and excited-state dipole moments and the difference thereof are, for the first time, obtained both experimentally and theoretically using solvatochromic equations and DFT/B3LYP/QZVP calculations. The approach is suggested to be promising and easily accessible, and can be universal to elucidate the electronic properties of metal-based compounds.

Electronic properties of diphenyl-s-tetrazine and some related oligomers. An spectroscopic and theoretical study

NASA Astrophysics Data System (ADS)

Moral, Mónica; García, Gregorio; Peñas, Antonio; Garzón, Andrés; Granadino-Roldán, José M.; Melguizo, Manuel; Fernández-Gómez, Manuel

2012-10-01

This work presents a theoretical and spectroscopic study on the electronic and structural properties of the diphenyl-s-tetrazine molecule (Ph2Tz) and some oligomeric derivatives. Ph2Tz was synthesized through a variation of Pinner-type reaction which uses N-acetylcysteine as catalyst. Insight into the structure and electronic properties of the title compound was obtained through IR, Raman, UV-Vis spectra in different solvents, and theoretical calculations. Theoretical studies have been extended to different n-mers derivatives up to an ideal molecular wire through the oligomeric approximation, predicting this way electronic properties such as LUMO energy levels, electron affinity and reorganization energy in order to assess their possible applications in molecular electronics.

Crystallographic and theoretical studies of an inclusion complex of β-cyclodextrin with fentanyl.

PubMed

Ogawa, Noriko; Nagase, Hiromasa; Loftsson, Thorsteinn; Endo, Tomohiro; Takahashi, Chisato; Kawashima, Yoshiaki; Ueda, Haruhisa; Yamamoto, Hiromitsu

2017-10-15

The crystal structure of an inclusion complex of β-cyclodextrin (β-CD) with fentanyl was determined by single crystal X-ray diffraction analysis. The crystal belongs to the triclinic space group P1 and the complex comprises one fentanyl, two β-CD, and several water molecules. β-CD and fentanyl form a host-guest inclusion complex at a ratio of 2:1 and the asymmetric unit of the complex contains two host molecules (β-CDs) in a head-to-head arrangement that form dimers through hydrogen bonds between the secondary hydroxyl groups of β-CD and one guest molecule. Fentanyl is totally contained within the β-CD cavity and the structure of the phenylethyl part of fentanyl inside the dimeric cavity of the complex is disordered. Furthermore, theoretical molecular conformational calculations were conducted to clarify the mobility of the guest molecule in the β-CD cavity using CONFLEX software. Crystal optimization and crystal energy calculations were also conducted. The results of the theoretical calculations confirmed that the conformation of disorder part 1, which was high in occupancy by crystal structure analysis, was more stable. The phenylethyl part of fentanyl existed in several stable conformations. Copyright © 2017 Elsevier B.V. All rights reserved.

Advanced seasonal reproductive development in a male urban bird is reflected in earlier plasma luteinizing hormone rise but not energetic status.

PubMed

Davies, Scott; Behbahaninia, Hirbod; Giraudeau, Mathieu; Meddle, Simone L; Waites, Kyle; Deviche, Pierre

2015-12-01

Urban animals inhabit an environment considerably different than do their non-urban conspecifics, and to persist urban animals must adjust to these novel environments. The timing of seasonal reproductive development (i.e., growth of gonads and secondary sex organs) is a fundamental determinant of the breeding period and is frequently advanced in urban bird populations. However, the underlying mechanism(s) by which birds adjust the timing of reproductive development to urban areas remain(s) largely unknown. Here, we compared the timing of vernal reproductive development in free-ranging urban and non-urban male Abert's Towhees, Melozone aberti, in Phoenix, Arizona, USA, and tested the non-mutually exclusive hypotheses that earlier reproductive development is due to improved energetic status and/or earlier increase in endocrine activity of the reproductive system. We found that urban birds initiated testicular development earlier than non-urban birds, but this disparity was not associated with differences in body condition, fat stores, or innate immune performance. These results provide no support for the hypothesis that energetic constraints are responsible for delayed reproductive development of non-urban relative to urban male Abert's Towhees. Urban birds did, however, increase their plasma luteinizing hormone, but not plasma testosterone, earlier than non-urban birds. These findings suggest that adjustment to urban areas by Abert's Towhees involves increases in the endocrine activity of the anterior pituitary gland and/or hypothalamus earlier than non-urban towhees. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Experimental (FT-IR, FT-Raman, 1H NMR) and theoretical study of magnesium, calcium, strontium, and barium picolinates.

PubMed

Swiderski, G; Kalinowska, M; Wojtulewski, S; Lewandowski, W

2006-05-01

The experimental IR, Raman, and 1H NMR spectra of picolinic acid, as well as magnesium, calcium, strontium, and barium picolinates were registered, assigned and studied. Characteristic changes in the spectra of metal picolinates in comparison with the spectrum of ligand were observed, which lead to the conclusion that perturbation of the aromatic system of picolinates increases along with the series Mg-->Ca-->Sr-->Ba. Theoretical structures of beryllium and magnesium picolinates, as well as theoretical IR spectrum of magnesium picolinate were calculated in B3PW91/6-311++G(d, p) level. On the basis of calculated bond lengths in pyridine ring geometric, aromaticity indexes HOMA were calculated. The idea of these indexes is based on the fact that the essential factor in aromatic stabilization is the pi delocalization manifested in: planar geometry, equalization of the bond lengths and angles, and symmetry. The decidedly lower value of HOMA for magnesium picolinate (i.e. 0.545; 0.539) than that for beryllium picolinate (i.e. 0.998; 0.998) indicate higher aromatic properties of Be picolinate than of Mg picolinate. The comparison of theoretical and literature experimental structures of magnesium picolinate was done. The experimental structure contains two water molecules, so the calculations for hydrated magnesium picolinate were carried on, and the influence of coordinated water molecule on the structure of picolinates was discussed. The HOMAs for hydrated experimental and calculated Mg picolinate amount to 0.870; 0.743, and 0.900; 0.890, respectively, whereas for anhydrous structure, it is as described above, i.e. 0.545; 0.539. Thus, the calculations clearly showed that water molecules coordinated to the central atom weakens the effect of metal on the electronic system of ligand.

Experimental (FT-IR, FT-Raman, 1H NMR) and theoretical study of magnesium, calcium, strontium, and barium picolinates

NASA Astrophysics Data System (ADS)

Świderski, G.; Kalinowska, M.; Wojtulewski, S.; Lewandowski, W.

2006-05-01

The experimental IR, Raman, and 1H NMR spectra of picolinic acid, as well as magnesium, calcium, strontium, and barium picolinates were registered, assigned and studied. Characteristic changes in the spectra of metal picolinates in comparison with the spectrum of ligand were observed, which lead to the conclusion that perturbation of the aromatic system of picolinates increases along with the series Mg → Ca → Sr → Ba. Theoretical structures of beryllium and magnesium picolinates, as well as theoretical IR spectrum of magnesium picolinate were calculated in B3PW91/6-311++G(d, p) level. On the basis of calculated bond lengths in pyridine ring geometric, aromaticity indexes HOMA were calculated. The idea of these indexes is based on the fact that the essential factor in aromatic stabilization is the π delocalization manifested in: planar geometry, equalization of the bond lengths and angles, and symmetry. The decidedly lower value of HOMA for magnesium picolinate (i.e. 0.545; 0.539) than that for beryllium picolinate (i.e. 0.998; 0.998) indicate higher aromatic properties of Be picolinate than of Mg picolinate. The comparison of theoretical and literature experimental structures of magnesium picolinate was done. The experimental structure contains two water molecules, so the calculations for hydrated magnesium picolinate were carried on, and the influence of coordinated water molecule on the structure of picolinates was discussed. The HOMAs for hydrated experimental and calculated Mg picolinate amount to 0.870; 0.743, and 0.900; 0.890, respectively, whereas for anhydrous structure, it is as described above, i.e. 0.545; 0.539. Thus, the calculations clearly showed that water molecules coordinated to the central atom weakens the effect of metal on the electronic system of ligand.

Theoretical study on the mechanism of the gas-phase elimination kinetics of alkyl chloroformates

NASA Astrophysics Data System (ADS)

Alcázar, Jackson J.; Marquez, Edgar; Mora, José R.; Cordova-Sintjago, Tania; Chuchani, Gabriel

2016-03-01

The theoretical calculations on the mechanism of the homogeneous and unimolecular gas-phase elimination kinetics of alkyl chloroformates- ethyl chloroformate (ECF), isopropyl chloroformate (ICF), and sec-butyl chloroformate (SCF) - have been carried out by using CBS-QB3 level of theory and density functional theory (DFT) functionals CAM-B3LYP, M06, MPW1PW91, and PBE1PBE with the basis sets 6-311++G(d,p) and 6-311++G(2d,2p). The chlorofomate compounds with alkyl ester Cβ-H bond undergo thermal decomposition producing the corresponding olefin, HCl and CO2. These homogeneous eliminations are proposed to undergo two different types of mechanisms: a concerted process, or via the formation of an unstable intermediate chloroformic acid (ClCOOH), which rapidly decomposes to HCl and CO2 gas. Since both elimination mechanisms may occur through a six-membered cyclic transition state structure, it is difficult to elucidate experimentally which is the most reasonable reaction mechanism. Theoretical calculations show that the stepwise mechanism with the formation of the unstable intermediate chloroformic acid from ECF, ICF, and SCF is favoured over one-step elimination. Reasonable agreements were found between theoretical and experimental values at the CAM-B3LYP/6-311++G(d,p) level.

Calculated and scale model experimentally measured scattering from metallic structures in Instrument Landing System

DOT National Transportation Integrated Search

1974-03-01

Comparison is made of theoretically calculated and experimentally determined scattering from metallic tilted rectangles and vertical cylindrical scatterers. The scattering was experimentally measured in a scale model range at the Watertown Arsenal, W...

Optimal pacing strategy: from theoretical modelling to reality in 1500-m speed skating.

PubMed

Hettinga, F J; De Koning, J J; Schmidt, L J I; Wind, N A C; Macintosh, B R; Foster, C

2011-01-01

Athletes are trained to choose the pace which is perceived to be correct during a specific effort, such as the 1500-m speed skating competition. The purpose of the present study was to "override" self-paced (SP) performance by instructing athletes to execute a theoretically optimal pacing profile. Seven national-level speed-skaters performed a SP 1500-m which was analysed by obtaining velocity (every 100 m) and body position (every 200 m) with video to calculate total mechanical power output. Together with gross efficiency and aerobic kinetics, obtained in separate trials, data were used to calculate aerobic and anaerobic power output profiles. An energy flow model was applied to SP, simulating a range of pacing strategies, and a theoretically optimal pacing profile was imposed in a second race (IM). Final time for IM was ∼2 s slower than SP. Total power distribution per lap differed, with a higher power over the first 300 m for IM (637.0 (49.4) vs 612.5 (50.0) W). Anaerobic parameters did not differ. The faster first lap resulted in a higher aerodynamic drag coefficient and perhaps a less effective push-off. Experienced athletes have a well-developed performance template, and changing pacing strategy towards a theoretically optimal fast start protocol had negative consequences on speed-skating technique and did not result in better performance.

Experimental and theoretical oscillator strengths of Mg I for accurate abundance analysis

NASA Astrophysics Data System (ADS)

Pehlivan Rhodin, A.; Hartman, H.; Nilsson, H.; Jönsson, P.

2017-02-01

Context. With the aid of stellar abundance analysis, it is possible to study the galactic formation and evolution. Magnesium is an important element to trace the α-element evolution in our Galaxy. For chemical abundance analysis, such as magnesium abundance, accurate and complete atomic data are essential. Inaccurate atomic data lead to uncertain abundances and prevent discrimination between different evolution models. Aims: We study the spectrum of neutral magnesium from laboratory measurements and theoretical calculations. Our aim is to improve the oscillator strengths (f-values) of Mg I lines and to create a complete set of accurate atomic data, particularly for the near-IR region. Methods: We derived oscillator strengths by combining the experimental branching fractions with radiative lifetimes reported in the literature and computed in this work. A hollow cathode discharge lamp was used to produce free atoms in the plasma and a Fourier transform spectrometer recorded the intensity-calibrated high-resolution spectra. In addition, we performed theoretical calculations using the multiconfiguration Hartree-Fock program ATSP2K. Results: This project provides a set of experimental and theoretical oscillator strengths. We derived 34 experimental oscillator strengths. Except from the Mg I optical triplet lines (3p 3P°0,1,2-4s 3S1), these oscillator strengths are measured for the first time. The theoretical oscillator strengths are in very good agreement with the experimental data and complement the missing transitions of the experimental data up to n = 7 from even and odd parity terms. We present an evaluated set of oscillator strengths, gf, with uncertainties as small as 5%. The new values of the Mg I optical triplet line (3p 3P°0,1,2-4s 3S1) oscillator strength values are 0.08 dex larger than the previous measurements.

Python for Information Theoretic Analysis of Neural Data

PubMed Central

Ince, Robin A. A.; Petersen, Rasmus S.; Swan, Daniel C.; Panzeri, Stefano

2008-01-01

Information theory, the mathematical theory of communication in the presence of noise, is playing an increasingly important role in modern quantitative neuroscience. It makes it possible to treat neural systems as stochastic communication channels and gain valuable, quantitative insights into their sensory coding function. These techniques provide results on how neurons encode stimuli in a way which is independent of any specific assumptions on which part of the neuronal response is signal and which is noise, and they can be usefully applied even to highly non-linear systems where traditional techniques fail. In this article, we describe our work and experiences using Python for information theoretic analysis. We outline some of the algorithmic, statistical and numerical challenges in the computation of information theoretic quantities from neural data. In particular, we consider the problems arising from limited sampling bias and from calculation of maximum entropy distributions in the presence of constraints representing the effects of different orders of interaction in the system. We explain how and why using Python has allowed us to significantly improve the speed and domain of applicability of the information theoretic algorithms, allowing analysis of data sets characterized by larger numbers of variables. We also discuss how our use of Python is facilitating integration with collaborative databases and centralised computational resources. PMID:19242557

Theoretical Evaluation of Crosslink Density of Chain Extended Polyurethane Networks Based on Hydroxyl Terminated Polybutadiene and Butanediol and Comparison with Experimental Data

NASA Astrophysics Data System (ADS)

Sekkar, Venkataraman; Alex, Ancy Smitha; Kumar, Vijendra; Bandyopadhyay, G. G.

2018-01-01

Polyurethane networks between hydroxyl terminated polybutadiene (HTPB) and butanediol (BD) were prepared using toluene diisocyanate (TDI) as the curative. HTPB and BD were taken at equivalent ratios viz.: 1:0, 1:1, 1:2, 1:4, and 1:8. Crosslink density (CLD) was theoretically calculated using α-model equations developed by Marsh. CLD for the polyurethane networks was experimentally evaluated from equilibrium swell and stress-strain data. Young's modulus and Mooney-Rivlin approaches were adopted to calculate CLD from stress-strain data. Experimentally obtained CLD values were enormously higher than theoretical values especially at higher BD/HTPB equivalent ratios. The difference in the theoretical and experimental values for CLD was explained in terms of local crystallization due to the formation of hard segments and hydrogen bonded interactions.

5 CFR Appendix A to Subpart C of... - Present Value Conversion Factors for Earlier Commencing Date of Annuities of Current and Former...

Code of Federal Regulations, 2010 CFR

2010-01-01

... 5 Administrative Personnel 2 2010-01-01 2010-01-01 false Present Value Conversion Factors for Earlier Commencing Date of Annuities of Current and Former Spouses of Deceased Separated Employees A...—Present Value Conversion Factors for Earlier Commencing Date of Annuities of Current and Former Spouses of...

Organized screening detects breast cancer at earlier stage regardless of molecular phenotype.

PubMed

Holloway, Claire M B; Jiang, Li; Whitehead, Marlo; Racz, Jennifer M; Groome, Patti A

2018-06-16

Mortality reduction attributable to organized breast screening is modest. Screening may be less effective at detecting more aggressive cancers at an earlier stage. This study was conducted to determine the relative efficacy of screening mammography to detect cancers at an earlier stage by molecular phenotype. We identified 2882 women with primary invasive breast cancer diagnosed between January 1, 2008 and December 31, 2012 and who had a mammogram through the Ontario Breast Screening Program in the 28 months before diagnosis. Five tumor phenotypes were defined by expression of estrogen (ER) and progesterone (PR) receptors and HER2/neu oncogene. We conducted univariable and multivariable analyses to describe the predictors of detection as an interval cancer. Additional analyses identified predictors of detection at stages II, III, or IV compared with stage I, by phenotype. Analyses were adjusted for the effects of age, grade, and breast density. ER negative and HER2 positive tumors were over-represented among interval cancers, and triple negative cancers were more likely than ER +/HER2 - cancers to be detected as interval cancers OR 2.5 (95% CI 2.0-3.2, p < 0.0001). Method of detection (interval vs. screen) and molecular phenotype were independently associated with stage at diagnosis (p < 0.0001), but there was no interaction between method of detection and phenotype (p = 0.44). In a screened population, triple negative and HER2 + breast cancers are diagnosed at a higher stage but this appears to be due to higher growth rates of these tumors rather than a relative inability of screening to detect them.

Flutter calculations in three degrees of freedom

NASA Technical Reports Server (NTRS)

Theodorsen, Theodore; Garrick, I E

1942-01-01

The present paper is a continuation of the general study of flutter published in NACA reports nos. 496 and 685. The paper is mainly devoted to flutter in three degrees of freedom (bending, torsion, and aileron) for which a number of selected cases have been calculated and presented in graphical form. The results are analyzed and discussed with regard to the effects of structural damping, of fractional-span ailerons, and of mass-balancing. The analysis shows that more emphasis should be put on the effect of structural damping and less on mass-balancing. The conclusion is drawn that a definite minimum amount of structural damping, which is usually found to be present, is essential in the calculations for an adequate description of the flutter case. Theoretical flutter predictions are thus brought into closer agreement with the facts of experience. A brief discussion is included of a particular biplane that had experienced flutter at about 200 miles per hour. Some simplifications have been achieved in the method of calculation. (author)

Quantum-mechanical calculations of magnesium aspartate arginine structure and spectroscopic characteristics

NASA Astrophysics Data System (ADS)

Marcoin, W.; Pasterny, K.; Wrzalik, R.

2005-05-01

Theoretical calculations of magnesium aspartate-arginine (Mg[Asp-Arg]) structure and spectroscopic characteristics have been performed in the gas phase with the GAUSSIAN 98 software package using density functional theory (DFT) at the B3PW91 level. The 6-31+G* basis set was selected due to their reasonable quality and size. The comparison with corresponding results for magnesium aspartate-glycine (Mg[Asp-Gly]) is presented. NMR and IR measurements were carried out and obtained experimental 1H and 13C chemical shifts and IR spectra are compared with calculated spectral parameters.

A primary care Web-based Intervention Modeling Experiment replicated behavior changes seen in earlier paper-based experiment.

PubMed

Treweek, Shaun; Francis, Jill J; Bonetti, Debbie; Barnett, Karen; Eccles, Martin P; Hudson, Jemma; Jones, Claire; Pitts, Nigel B; Ricketts, Ian W; Sullivan, Frank; Weal, Mark; MacLennan, Graeme

2016-12-01

Intervention Modeling Experiments (IMEs) are a way of developing and testing behavior change interventions before a trial. We aimed to test this methodology in a Web-based IME that replicated the trial component of an earlier, paper-based IME. Three-arm, Web-based randomized evaluation of two interventions (persuasive communication and action plan) and a "no intervention" comparator. The interventions were designed to reduce the number of antibiotic prescriptions in the management of uncomplicated upper respiratory tract infection. General practitioners (GPs) were invited to complete an online questionnaire and eight clinical scenarios where an antibiotic might be considered. One hundred twenty-nine GPs completed the questionnaire. GPs receiving the persuasive communication did not prescribe an antibiotic in 0.70 more scenarios (95% confidence interval [CI] = 0.17-1.24) than those in the control arm. For the action plan, GPs did not prescribe an antibiotic in 0.63 (95% CI = 0.11-1.15) more scenarios than those in the control arm. Unlike the earlier IME, behavioral intention was unaffected by the interventions; this may be due to a smaller sample size than intended. A Web-based IME largely replicated the findings of an earlier paper-based study, providing some grounds for confidence in the IME methodology. Copyright © 2016 Elsevier Inc. All rights reserved.

Bayesian sample size calculations in phase II clinical trials using a mixture of informative priors.

PubMed

Gajewski, Byron J; Mayo, Matthew S

2006-08-15

A number of researchers have discussed phase II clinical trials from a Bayesian perspective. A recent article by Mayo and Gajewski focuses on sample size calculations, which they determine by specifying an informative prior distribution and then calculating a posterior probability that the true response will exceed a prespecified target. In this article, we extend these sample size calculations to include a mixture of informative prior distributions. The mixture comes from several sources of information. For example consider information from two (or more) clinicians. The first clinician is pessimistic about the drug and the second clinician is optimistic. We tabulate the results for sample size design using the fact that the simple mixture of Betas is a conjugate family for the Beta- Binomial model. We discuss the theoretical framework for these types of Bayesian designs and show that the Bayesian designs in this paper approximate this theoretical framework. Copyright 2006 John Wiley & Sons, Ltd.

Measurements and calculations of transport AC loss in second generation high temperature superconducting pancake coils

NASA Astrophysics Data System (ADS)

Yuan, Weijia; Coombs, T. A.; Kim, Jae-Ho; Han Kim, Chul; Kvitkovic, Jozef; Pamidi, Sastry

2011-12-01

Theoretical and experimental AC loss data on a superconducting pancake coil wound using second generation (2 G) conductors are presented. An anisotropic critical state model is used to calculate critical current and the AC losses of a superconducting pancake coil. In the coil there are two regions, the critical state region and the subcritical region. The model assumes that in the subcritical region the flux lines are parallel to the tape wide face. AC losses of the superconducting pancake coil are calculated using this model. Both calorimetric and electrical techniques were used to measure AC losses in the coil. The calorimetric method is based on measuring the boil-off rate of liquid nitrogen. The electric method used a compensation circuit to eliminate the inductive component to measure the loss voltage of the coil. The experimental results are consistent with the theoretical calculations thus validating the anisotropic critical state model for loss estimations in the superconducting pancake coil.

Simplified Calculation Model and Experimental Study of Latticed Concrete-Gypsum Composite Panels

PubMed Central

Jiang, Nan; Ma, Shaochun

2015-01-01

In order to address the performance complexity of the various constituent materials of (dense-column) latticed concrete-gypsum composite panels and the difficulty in the determination of the various elastic constants, this paper presented a detailed structural analysis of the (dense-column) latticed concrete-gypsum composite panel and proposed a feasible technical solution to simplified calculation. In conformity with mechanical rules, a typical panel element was selected and divided into two homogenous composite sub-elements and a secondary homogenous element, respectively for solution, thus establishing an equivalence of the composite panel to a simple homogenous panel and obtaining the effective formulas for calculating the various elastic constants. Finally, the calculation results and the experimental results were compared, which revealed that the calculation method was correct and reliable and could meet the calculation needs of practical engineering and provide a theoretical basis for simplified calculation for studies on composite panel elements and structures as well as a reference for calculations of other panels. PMID:28793631

Simplified Calculation Model and Experimental Study of Latticed Concrete-Gypsum Composite Panels.

PubMed

Jiang, Nan; Ma, Shaochun

2015-10-27

In order to address the performance complexity of the various constituent materials of (dense-column) latticed concrete-gypsum composite panels and the difficulty in the determination of the various elastic constants, this paper presented a detailed structural analysis of the (dense-column) latticed concrete-gypsum composite panel and proposed a feasible technical solution to simplified calculation. In conformity with mechanical rules, a typical panel element was selected and divided into two homogenous composite sub-elements and a secondary homogenous element, respectively for solution, thus establishing an equivalence of the composite panel to a simple homogenous panel and obtaining the effective formulas for calculating the various elastic constants. Finally, the calculation results and the experimental results were compared, which revealed that the calculation method was correct and reliable and could meet the calculation needs of practical engineering and provide a theoretical basis for simplified calculation for studies on composite panel elements and structures as well as a reference for calculations of other panels.

Theoretical and material studies on thin-film electroluminescent devices

NASA Technical Reports Server (NTRS)

Summers, C. J.; Brennan, K. F.

1986-01-01

A theoretical study of resonant tunneling in multilayered heterostructures is presented based on an exact solution of the Schroedinger equation under the application of a constant electric field. By use of the transfer matrix approach, the transmissivity of the structure is determined as a function of the incident electron energy. The approach presented is easily extended to many layer structures where it is more accurate than other existing transfer matrix or WKB models. The transmission resonances are compared to the bound state energies calculated for a finite square well under bias using either an asymmetric square well model or the exact solution of an infinite square well under the application of an electric field. The results show good agreement with other existing models as well as with the bound state energies. The calculations were then applied to a new superlattice structure, the variablly spaced superlattice energy filter, (VSSEP) which is designed such that under bias the spatial quantization levels fully align. Based on these calculations, a new class of resonant tunneling superlattice devices can be designed.

Multi-scale theoretical investigation of hydrogen storage in covalent organic frameworks.

PubMed

Tylianakis, Emmanuel; Klontzas, Emmanouel; Froudakis, George E

2011-03-01

The quest for efficient hydrogen storage materials has been the limiting step towards the commercialization of hydrogen as an energy carrier and has attracted a lot of attention from the scientific community. Sophisticated multi-scale theoretical techniques have been considered as a valuable tool for the prediction of materials storage properties. Such techniques have also been used for the investigation of hydrogen storage in a novel category of porous materials known as Covalent Organic Frameworks (COFs). These framework materials are consisted of light elements and are characterized by exceptional physicochemical properties such as large surface areas and pore volumes. Combinations of ab initio, Molecular Dynamics (MD) and Grand Canonical Monte-Carlo (GCMC) calculations have been performed to investigate the hydrogen adsorption in these ultra-light materials. The purpose of the present review is to summarize the theoretical hydrogen storage studies that have been published after the discovery of COFs. Experimental and theoretical studies have proven that COFs have comparable or better hydrogen storage abilities than other competitive materials such as MOF. The key factors that can lead to the improvement of the hydrogen storage properties of COFs are highlighted, accompanied with some recently presented theoretical multi-scale studies concerning these factors.

Theoretical calculations of Electron Paramagnetic Resonance parameters of liquid phase Orotic acid radical

NASA Astrophysics Data System (ADS)

Sarikaya, Ebru Karakaş; Dereli, Ömer

2017-02-01

To obtain liquid phase molecular structure, conformational analysis of Orotic acid was performed and six conformers were determined. For these conformations, eight possible radicals were modelled by using Density Functional Theory computations with respect to molecular structure. Electron Paramagnetic Resonance parameters of these model radicals were calculated and then they were compared with the experimental ones. Geometry optimizations of the molecule and modeled radicals were performed using Becke's three-parameter hybrid-exchange functional combined with the Lee-Yang-Parr correlation functional of Density Functional Theory and 6-311++G(d,p) basis sets in p-dioxane solution. Because Orotic acid can be mutagenic in mammalian somatic cells and it is also mutagenic for bacteria and yeast, it has been studied.

Theoretical investigation of the molecular structure of the isoquercitrin molecule

NASA Astrophysics Data System (ADS)

Cornard, J. P.; Boudet, A. C.; Merlin, J. C.

1999-09-01

Isoquercitrin is a glycosilated flavonoid that has received a great deal of attention because of its numerous biological effects. We present a theoretical study on isoquercitrin using both empirical (Molecular Mechanics (MM), with MMX force field) and quantum chemical (AM1 semiempirical method) techniques. The most stable structures of the molecule obtained by MM calculations have been used as input data for the semiempirical treatment. The position and orientation of the glucose moiety with regard to the remainder of the molecule have been investigated. The flexibility of isoquercitrin principally lies in rotations around the inter-ring bond and the sugar link. In order to know the structural modifications generated by the substitution by a sugar, geometrical parameters of quercetin (aglycon) and isoquercitrin have been compared. The good accordance between theoretical and experimental electronic spectra permits to confirm the reliability of the structural model.

Synthesis, spectroscopic and structural characterization of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine with theoretical calculations using density functional theory

NASA Astrophysics Data System (ADS)

İnkaya, Ersin; Dinçer, Muharrem; Şahan, Emine; Yıldırım, İsmail

2013-10-01

In this paper, we will report a combined experimental and theoretical investigation of the molecular structure and spectroscopic parameters (FT-IR, 1H NMR, 13C NMR) of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine. The compound crystallizes in the triclinic space group P-1 with Z = 2. The molecular geometry was also optimized using density functional theory (DFT/B3LYP) method with the 6-311G(d,p) and 6-311++G(d,p) basis sets in ground state and compared with the experimental data. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecules has been obtained by mapping electron density isosurface with electrostatic potential (ESP). Also, non-linear optical properties of the title compound were performed at B3LYP/6-311++G(d,p) level. The theoretical results showed an excellent agreement with the experimental values.

Theoretical Calculation of the Gas-Sensing Properties of Pt-Decorated Carbon Nanotubes

PubMed Central

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

2013-01-01

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

Vanadium supersaturated silicon system: a theoretical and experimental approach

NASA Astrophysics Data System (ADS)

Garcia-Hemme, Eric; García, Gregorio; Palacios, Pablo; Montero, Daniel; García-Hernansanz, Rodrigo; Gonzalez-Diaz, Germán; Wahnon, Perla

2017-12-01

The effect of high dose vanadium ion implantation and pulsed laser annealing on the crystal structure and sub-bandgap optical absorption features of V-supersaturated silicon samples has been studied through the combination of experimental and theoretical approaches. Interest in V-supersaturated Si focusses on its potential as a material having a new band within the Si bandgap. Rutherford backscattering spectrometry measurements and formation energies computed through quantum calculations provide evidence that V atoms are mainly located at interstitial positions. The response of sub-bandgap spectral photoconductance is extended far into the infrared region of the spectrum. Theoretical simulations (based on density functional theory and many-body perturbation in GW approximation) bring to light that, in addition to V atoms at interstitial positions, Si defects should also be taken into account in explaining the experimental profile of the spectral photoconductance. The combination of experimental and theoretical methods provides evidence that the improved spectral photoconductance up to 6.2 µm (0.2 eV) is due to new sub-bandgap transitions, for which the new band due to V atoms within the Si bandgap plays an essential role. This enables the use of V-supersaturated silicon in the third generation of photovoltaic devices.

Theoretical Infrared Spectra for Polycyclic Aromatic Hydrocarbon Neutrals, Cations and Anions

NASA Technical Reports Server (NTRS)

Langhoff, Stephen R.

1995-01-01

Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of the neutrals and cations of thirteen polycyclic aromatic hydrocarbons (PAHs) up to the size of ovalene. Calculations are also carried out for a few PAH anions. The DFT harmonic frequencies, when uniformly scaled by the factor of 0.958 to account primarily for anharmonicity, agree with the matrix isolation fundamentals to within an average error of about 10 per centimeter. Electron correlation is found to significantly reduce the intensities of many of the cation harmonics, bringing them into much better agreement with the available experimental data. While the theoretical infrared spectra agree well with the experimental data for the neutral systems and for many of the cations, there are notable discrepancies with the experimental matrix isolation data for some PAH cations that are difficult to explain in terms of limitations in the calculations. In agreement with previous theoretical work, the present calculations show that the relative intensities for the astronomical unidentified infrared (UIR) bands agree reasonably well with those for a distribution of polycyclic aromatic hydrocarbon (PAH) cations, but not with a distribution of PAH neutrals. We also observe that the infrared spectra of highly symmetrical cations such as coronene agree much better with astronomical observations than do those of, for example, the polyacenes such as tetracene and pentacene. The total integrated intensities for the neutral species are found to increase linearly with size, while the total integrated intensities are much larger for the cations and scale more nearly quadratically with size. We conclude that emission from moderate-sized highly symmetric PAH cations such as coronene and larger could account for the UIR bands.

Impact cratering calculations

NASA Technical Reports Server (NTRS)

Ahrens, Thomas J.; Okeefe, J. D.; Smither, C.; Takata, T.

1991-01-01

In the course of carrying out finite difference calculations, it was discovered that for large craters, a previously unrecognized type of crater (diameter) growth occurred which was called lip wave propagation. This type of growth is illustrated for an impact of a 1000 km (2a) silicate bolide at 12 km/sec (U) onto a silicate half-space at earth gravity (1 g). The von Misses crustal strength is 2.4 kbar. The motion at the crater lip associated with this wave type phenomena is up, outward, and then down, similar to the particle motion of a surface wave. It is shown that the crater diameter has grown d/a of approximately 25 to d/a of approximately 4 via lip propagation from Ut/a = 5.56 to 17.0 during the time when rebound occurs. A new code is being used to study partitioning of energy and momentum and cratering efficiency with self gravity for finite-sized objects rather than the previously discussed planetary half-space problems. These are important and fundamental subjects which can be addressed with smoothed particle hydrodynamic (SPH) codes. The SPH method was used to model various problems in astrophysics and planetary physics. The initial work demonstrates that the energy budget for normal and oblique impacts are distinctly different than earlier calculations for silicate projectile impact on a silicate half space. Motivated by the first striking radar images of Venus obtained by Magellan, the effect of the atmosphere on impact cratering was studied. In order the further quantify the processes of meteor break-up and trajectory scattering upon break-up, the reentry physics of meteors striking Venus' atmosphere versus that of the Earth were studied.

Economic Costs Avoided by Diagnosing Melanoma Six Months Earlier Justify >100 Benign Biopsies.

PubMed

Aires, Daniel J; Wick, Jo; Shaath, Tarek S; Rajpara, Anand N; Patel, Vikas; Badawi, Ahmed H; Li, Cicy; Fraga, Garth R; Doolittle, Gary; Liu, Deede Y

2016-05-01

New melanoma drugs bring enormous benefits but do so at significant costs. Because melanoma grows deeper and deadlier over time, deeper lesions are costlier due to increased sentinel lymph node biopsy, chemotherapy, and disease-associated income loss. Prior studies have justified pigmented lesion biopsies on a "value per life" basis; by contrast we sought to assess how many biopsies are justified per melanoma found on a purely economic basis. We modeled how melanomas in the United States would behave if diagnosis were delayed by 6 months, eg, not biopsied, only observed until the next surveillance visit. Economic loss from delayed biopsy is the obverse of economic benefit of performing biopsy earlier. Growth rates were based on Liu et al. The results of this study can be applied to all patients presenting to dermatologists with pigmented skin lesions suspicious for melanoma. In-situ melanomas were excluded because no studies to date have modeled growth rates analogous to those for invasive melanoma. We assume conservatively that all melanomas not biopsied initially will be biopsied and treated 6 months later. Major modeled costs are (1) increased sentinel lymph node biopsy, (2) increased chemotherapy for metastatic lesions using increased 5-yr death as metastasis marker, and (3) income loss per melanoma death at $413,370 as previously published. Costs avoided by diagnosing melanoma earlier justify 170 biopsies per melanoma found. Efforts to penalize "unnecessary" biopsies may be economically counterproductive.

J Drugs Dermatol. 2016;15(5):527-532.

Delusions and underlying needs in older adults with Alzheimer's disease: influence of earlier life experiences and the current environment.

PubMed

Wang, Jing-Jy; Cheng, Wen-Yun; Lai, Pei-Ru; Pai, Ming-Chyi

2014-12-01

Delusions are one of the most severe psychiatric symptoms of individuals with Alzheimer's disease (AD), which often increase the stress experienced by caregivers. The purpose of this study was to understand the influences of earlier life experiences and the current environment on delusions, as well as the underlying needs of older adults with AD who experience delusions. Using an exploratory research design with a qualitative approach and purposive sampling, 20 family caregivers were interviewed. Two psychosocial types of attributes of delusion were categorized: Type A, the influence of earlier life experiences; and Type B, current environmental influences. The underlying needs of those with delusions include physical comfort, a desire to be secure, and a sense of belonging. The contents of delusions are easily influenced by patients' earlier negative experiences and responsibilities, whereas the current environment exerts a crucial influence on the occurrence, frequency, and severity of specific delusions. These results can facilitate planning for patient-centered care by enhancing health care providers' understanding of the psychosocial and environmental attributes and needs behind delusions. Copyright 2014, SLACK Incorporated.

Binding of urea and thiourea with a barbiturate derivative: experimental and theoretical approach.

PubMed

Dixit, Namrata; Shukla, P K; Mishra, P C; Mishra, Lallan; Roesky, Herbert W

2010-01-14

A barbiturate derivative [1,5-dihydro-5-[5-pyrimidine-2,4(1H,3H)-dionyl]-2H-chromeno[2,3-d] pyrimidine-2,4(3H)-dione)] (L1) possesses functionalities complementary to amide and thioamide. Hence its binding with urea and thiourea, is monitored using UV-vis and fluorescence titrations as well as isothermal titration calorimetry (ITC) study. Theoretical studies on hydrogen-bonded complexes of L1-urea and L1-thiourea in the gas phase, aqueous, and DMSO medium are carried out using density functional theory (DFT) at the B3LYP/6-31G** level. The theoretical calculations support the experimental results.

The association between cannabis use and earlier age at onset of schizophrenia and other psychoses: meta-analysis of possible confounding factors.

PubMed

Myles, Nicholas; Newall, Hannah; Nielssen, Olav; Large, Matthew

2012-01-01

A recent meta-analysis showed that the mean age of onset of psychosis among cannabis users was almost three years earlier than that of non-cannabis users. However, because cannabis users usually smoke tobacco, the use of tobacco might independently contribute to the earlier onset of psychosis. We aimed to use meta-analysis to compare the extent to which cannabis and tobacco use are each associated with an earlier age at onset of schizophrenia and other psychoses. We also examined other factors that might have contributed to the finding of an earlier age of onset among cannabis users, including the proportion of males in the samples, the diagnostic inclusion criteria and aspects of study quality. The electronic databases MEDLINE, EMBASE, PsycINFO and ISI Web of Science, were searched for English-language peer-reviewed publications that reported age at onset of schizophrenia and other psychoses separately for cannabis users and non-users, or for tobaccosmokers and non-smokers. Meta-analysis showed that the age at onset of psychosis for cannabis users was 32 months earlier than for cannabis non-users (SMD=- 0.399, 95%CI -0.493 - -0.306, z=-8.34, p < 0.001), and was two weeks later in tobacco smokers compared with non-smokers (SMD=0.002, 95%CI -0.094 - 0.097, z=0.03, p=0.974). The main results were not affected by subgroup analyses examining studies of a single sex, the methods for making psychiatric diagnoses and measures of study quality. The results suggest that the association between cannabis use and earlier onset of psychosis is robust and is not the result either of tobacco smoking by cannabis using patients or the other potentially confounding factors we examined. This supports the hypothesis that, in some patients, cannabis use plays a causal role in the development of schizophrenia and raises the possibility of treating schizophrenia with new pharmacological treatments that have an affinity for endo-cannabinoid receptors.

When combined X-ray and polarized neutron diffraction data challenge high-level calculations: spin-resolved electron density of an organic radical.

PubMed

Voufack, Ariste Bolivard; Claiser, Nicolas; Lecomte, Claude; Pillet, Sébastien; Pontillon, Yves; Gillon, Béatrice; Yan, Zeyin; Gillet, Jean Michel; Marazzi, Marco; Genoni, Alessandro; Souhassou, Mohamed

2017-08-01

Joint refinement of X-ray and polarized neutron diffraction data has been carried out in order to determine charge and spin density distributions simultaneously in the nitronyl nitroxide (NN) free radical Nit(SMe)Ph. For comparison purposes, density functional theory (DFT) and complete active-space self-consistent field (CASSCF) theoretical calculations were also performed. Experimentally derived charge and spin densities show significant differences between the two NO groups of the NN function that are not observed from DFT theoretical calculations. On the contrary, CASSCF calculations exhibit the same fine details as observed in spin-resolved joint refinement and a clear asymmetry between the two NO groups.

A Theoretical Study on Seasonality

PubMed Central

Schmal, Christoph; Myung, Jihwan; Herzel, Hanspeter; Bordyugov, Grigory

2015-01-01

In addition to being endogenous, a circadian system must be able to communicate with the outside world and align its rhythmicity to the environment. As a result of such alignment, external Zeitgebers can entrain the circadian system. Entrainment expresses itself in coinciding periods of the circadian oscillator and the Zeitgeber and a stationary phase difference between them. The range of period mismatches between the circadian system and the Zeitgeber that Zeitgeber can overcome to entrain the oscillator is called an entrainment range. The width of the entrainment range usually increases with increasing Zeitgeber strength, resulting in a wedge-like Arnold tongue. This classical view of entrainment does not account for the effects of photoperiod on entrainment. Zeitgebers with extremely small or large photoperiods are intuitively closer to constant environments than equinoctial Zeitgebers and hence are expected to produce a narrower entrainment range. In this paper, we present theoretical results on entrainment under different photoperiods. We find that in the photoperiod-detuning parameter plane, the entrainment zone is shaped in the form of a skewed onion. The bottom and upper points of the onion are given by the free-running periods in DD and LL, respectively. The widest entrainment range is found near photoperiods of 50%. Within the onion, we calculated the entrainment phase that varies over a range of 12 h. The results of our theoretical study explain the experimentally observed behavior of the entrainment phase in dependence on the photoperiod. PMID:25999912

Vacuum ultraviolet photofragmentation of octadecane: photoionization mass spectrometric and theoretical investigation.

PubMed

Xu, Jing; Sang, Pengpeng; Zhao, Lianming; Guo, Wenyue; Qi, Fei; Xing, Wei; Yan, Zifeng

The photoionization and fragmentation of octadecane were investigated with infrared laser desorption/tunable synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (IRLD/VUV PIMS) and theoretical calculations. Mass spectra of octadecane were measured at various photon energies. The fragment ions were gradually detected with the increase of photon energy. The main fragment ions were assigned to radical ions (C n H 2 n +1 + , n  = 4-11) and alkene ions (C n H 2 n + , n  = 5-10). The ionization energy of the precursor and appearance energy of ionic fragments were obtained by measuring the photoionization efficiency spectrum. Possible formation pathways of the fragment ions were discussed with the help of density functional theory calculations.

Threshold collision-induced dissociation and theoretical study of protonated azobenzene

NASA Astrophysics Data System (ADS)

Rezaee, Mohammadreza; McNary, Christopher P.; Armentrout, P. B.

2017-10-01

Protonated azobenzene (AB), H+(C6H5N2C6H5), has been studied using threshold collision-induced dissociation in a guided ion beam tandem mass spectrometer. Product channels observed are C6H5N2+ + C6H6 and C6H5+ + N2 + C6H6. The experimental kinetic energy-dependent cross sections were analyzed using a statistical model that accounts for internal and kinetic energy distributions of the reactants, multiple collisions, and kinetic shifts. From this analysis, the activation energy barrier height of 2.02 ± 0.11 eV for benzene loss is measured. To identify the transition states (TSs) and intermediates (IMs) for these dissociations, relaxed potential energy surface (PES) scans were performed at the B3LYP/aug-cc-pVTZ level of theory. The PES indicates that there is a substantial activation energy along the dissociation reaction coordinate that is the rate-limiting step for benzene loss and at some levels of theory, for subsequent N2 loss as well. Relative energies of the reactant, TSs, IMs, and products were calculated at B3LYP, wB97XD, M06, PBEPBE, and MP2(full) levels of theory using both 6-311++G(2d,2p) and aug-cc-pVTZ basis sets. Comparison of the experimental results with theoretical values from various computational methods indicates how well these theoretical methods can predict thermochemical properties. In addition to these density functional theory and MP2 methods, several high accuracy multi-level calculations such as CBS-QB3, G3, G3MP2, G3B3MP2, G4, and G4MP2 were performed to determine the thermochemical properties of AB including the proton affinity and gas-phase basicity, and to compare the performance of different theoretical methods.

Resonant transfer excitation in collisions of F6+ and Mg9+ with H2

NASA Astrophysics Data System (ADS)

Bernstein, E. M.; Kamal, A.; Zaharakis, K. E.; Clark, M. W.; Tanis, J. A.; Ferguson, S. M.; Badnell, N. R.

1991-10-01

Experimental and theoretical investigations of resonant transfer excitation (RTE) for F6++H2 and Mg9++H2 collisions have been made. For both collision systems good agreement is obtained between the measured cross sections for K-shell x-ray emission coincident with electron-capture and theoretical RTE calculations. For F6+ the present calculations are about 10% lower than previous results of Bhalla and Karim [Phys. Rev. A 39, 6060 (1989); 41, 4097(E) (1990]; the measured cross sections are a factor of 2.3 larger than earlier measurements of Schulz et al. [Phys. Rev. A 38, 5454 (1988)]. The previous disagreement between experiment and theory for F6+ is removed.

Calculated hydroxyl A2 sigma --> X2 pi (0, 0) band emission rate factors applicable to atmospheric spectroscopy

NASA Technical Reports Server (NTRS)

Cageao, R. P.; Ha, Y. L.; Jiang, Y.; Morgan, M. F.; Yung, Y. L.; Sander, S. P.

1997-01-01

A calculation of the A2 sigma --> X2 pi (0, 0) band emission rate factors and line center absorption cross sections of OH applicable to its measurement using solar resonant fluorescence in the terrestrial atmosphere is presented in this paper. The most accurate available line parameters have been used. Special consideration has been given to the solar input flux because of its highly structured Fraunhofer spectrum. The calculation for the OH atmospheric emission rate factor in the solar resonant fluorescent case is described in detail with examples and intermediate results. Results of this calculation of OH emission rate factors for individual rotational lines are on average 30% lower than the values obtained in an earlier work.

Theoretical study of metal noble-gas positive ions

NASA Technical Reports Server (NTRS)

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

1989-01-01

Theoretical calculations have been performed to determine the spectroscopic constant for the ground and selected low-lying electronic states of the transition-metal noble-gas ions Var(+), FeAr(+), CoAr(+), CuHe(+), CuAr(+), and CuKr(+). Analogous calculations have been performed for the ground states of the alkali noble-gas ions LiAr(+), LiKr(+), NaAr(+), and KAr(+) and the alkaline-earth noble-gas ion MgAr(+) to contrast the difference in binding energies between the simple and transition-metal noble-gas ions. The binding energies increase with increasing polarizability of the noble-gas ions, as expected for a charge-induced dipole bonding mechanism. It is found that the spectroscopic constants of the X 1Sigma(+) states of the alkali noble-gas ions are well described at the self-consistent field level. In contrast, the binding energies of the transition-metal noble-gas ions are substantially increased by electron correlation.

Theoretical Conversions of Different Hardness and Tensile Strength for Ductile Materials Based on Stress-Strain Curves

NASA Astrophysics Data System (ADS)

Chen, Hui; Cai, Li-Xun

2018-04-01

Based on the power-law stress-strain relation and equivalent energy principle, theoretical equations for converting between Brinell hardness (HB), Rockwell hardness (HR), and Vickers hardness (HV) were established. Combining the pre-existing relation between the tensile strength ( σ b ) and Hollomon parameters ( K, N), theoretical conversions between hardness (HB/HR/HV) and tensile strength ( σ b ) were obtained as well. In addition, to confirm the pre-existing σ b -( K, N) relation, a large number of uniaxial tensile tests were conducted in various ductile materials. Finally, to verify the theoretical conversions, plenty of statistical data listed in ASTM and ISO standards were adopted to test the robustness of the converting equations with various hardness and tensile strength. The results show that both hardness conversions and hardness-strength conversions calculated from the theoretical equations accord well with the standard data.

Photoelectron Spectroscopic and Theoretical Study of B-16(-) and B-16(2-): An All-Boron Naphthalene

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

Sergeeva, Alina P.; Zubarev, Dmitry Y.; Zhai, Hua Jin

Although boron clusters were experimentally studied shortly after the discovery of the fullerenes, their structural characterization was only possible fairly recently when we combined photoelectron spectroscopy (PES) and theoretical calculations to investigate the structures and bonding of boron clusters. Early theoretical studies indicated that small boron clusters do not assume cage-like structures, which are common in bulk boron and compounds; instead, planar or quasi-planar structures were suggested. The combined PES and theoretical studies show indeed boron clusters with up to 15 atom are planar, and only at B20 does a three-dimensional (3D) structure (double ring) become energetically competitive, whereas B20-more » still remains planar. A recent ion mobility and theoretical study showed that for Bn + the doublering 3D structure becomes competitive at B16 +7.« less

Theoretical study on elastic properties of Si2N2O by ab initio calculation

NASA Astrophysics Data System (ADS)

Tsuboi, Seiya; Adachi, Kanta; Nagakubo, Akira; Ogi, Hirotsugu

2018-07-01

The elastic constants of crystalline Si2N2O remain unknown since it was discovered in the 1960s. We determine the nine independent elastic constants of orthorhombic Si2N2O by ab initio calculations. We applied various deformation modes with strains up to ±0.01 to a unit cell, calculated the energy-strain relationships, and deduced all the elastic constants by fitting the harmonic-oscillation function. Our results are as follows: C 11 = 311.1, C 22 = 238.5, C 33 = 317.9, C 44 = 136.1, C 55 = 57.6, C 66 = 73.9, C 12 = 79.6, C 13 = 52.2, and C 23 = 33.6 GPa. Despite the different crystal structures and symmetries, the direction-over-averaged Young’s modulus of Si2N2O is well explained by the nitrogen content and Young’s moduli of α-SiO2 and β-Si3N4. The anisotropy of sound-wave velocity was investigated, and its origin was examined on the basis of the crystallographic structure. The quasi-isotropic plane for the longitudinal-wave propagation was identified.

37 CFR 1.78 - Claiming benefit of earlier filing date and cross-references to other applications.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 37 Patents, Trademarks, and Copyrights 1 2014-07-01 2014-07-01 false Claiming benefit of earlier filing date and cross-references to other applications. 1.78 Section 1.78 Patents, Trademarks, and Copyrights UNITED STATES PATENT AND TRADEMARK OFFICE, DEPARTMENT OF COMMERCE GENERAL RULES OF PRACTICE IN...

37 CFR 1.78 - Claiming benefit of earlier filing date and cross-references to other applications.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 37 Patents, Trademarks, and Copyrights 1 2011-07-01 2011-07-01 false Claiming benefit of earlier filing date and cross-references to other applications. 1.78 Section 1.78 Patents, Trademarks, and Copyrights UNITED STATES PATENT AND TRADEMARK OFFICE, DEPARTMENT OF COMMERCE GENERAL RULES OF PRACTICE IN...

Theoretical and experimental studies on vibrational and nonlinear optic properties of guanidinium 3-nitrobenzoate. Differences and similarity between guanidinium 3-nitrobenzoate and guanidinium 4-nitrobenzoate complexes

NASA Astrophysics Data System (ADS)

Drozd, Marek

2018-03-01

According to literature data two structures of guanidine with nitrobenzoic acids are known. For guanidinium 4-nitrobenzoate the detailed studies of X-ray structure, vibrational and theoretical properties were performed. This compound was classified as second harmonic generator with efficiency of 3.3 times that KDP, standard crystal. On the contrary to mentioned above results for the guanidinium 3-nitrobenzoate the basic X-ray diffraction study was performed, only. On the basis of established crystallographic results, the detailed investigation of geometry and vibrational properties were made on the basis of theoretical calculation. According to this data the equilibrium geometry of investigated molecule was established. On the basis of this calculation the detailed computational studies of vibrational properties were performed. The theoretical IR and Raman frequencies, intensities and PED analysis are presented. Additionally, the NBO charges, HOMO and LUMO shapes and NLO properties of titled crystal were calculated. On the basis of these results the crystal was classified as second order generator in NLO but with bigger efficiency that guanidinium 4-nitorobenzoate compound. The obtained data are compared with experimental crystallographic and vibrational results for real crystal of guanidinium 3-nitrobenzoate. Additionally, the theoretical vibrational spectra are compared with literature calculations of guanidinium 4-nitrobenzoate compound.

Determination of absolute configuration of natural products: theoretical calculation of electronic circular dichroism as a tool

USDA-ARS?s Scientific Manuscript database

Determination of absolute configuration (AC) is one of the most challenging features in the structure elucidation of chiral natural products, especially those with complex structures. With revolutionary advancements in the area of quantum chemical calculations of chiroptical spectroscopy over the pa...

Inelastic Tunneling Spectroscopy of Alkanethiol Molecules: High-Resolution Spectroscopy and Theoretical Simulations

NASA Astrophysics Data System (ADS)

Okabayashi, Norio; Paulsson, Magnus; Ueba, Hiromu; Konda, Youhei; Komeda, Tadahiro

2010-02-01

We investigate inelastic electron tunneling spectroscopy (IETS) for alkanethiol self-assembled monolayers (SAM) with a scanning tunneling microscope and compare it to first-principles calculations. Using a combination of partial deuteration of the molecule and high-resolution measurements, we identify and differentiate between methyl (CH3) and methylene (CH2) groups and their symmetric and asymmetric C-H stretch modes. The calculations agree quantitatively with the measured IETS in producing the weight of the symmetric and asymmetric C-H stretch modes while the methylene stretch mode is largely underestimated. We further show that inelastic intermolecular scattering is important in the SAM by plotting the theoretical current densities.

Demonstration of theoretical and experimental simulations in fiber optics course

NASA Astrophysics Data System (ADS)

Yao, Tianfu; Wang, Xiaolin; Shi, Jianhua; Lei, Bing; Liu, Wei; Wang, Wei; Hu, Haojun

2017-08-01

"Fiber optics" course plays a supporting effect in the curriculum frame of optics and photonics at both undergraduate and postgraduate levels. Moreover, the course can be treated as compulsory for students specialized in the fiber-related field, such as fiber communication, fiber sensing and fiber light source. The corresponding content in fiber optics requires the knowledge of geometrical and physical optics as background, including basic optical theory and fiber components in practice. Thus, to help the students comprehend the relatively abundant and complex content, it is necessary to investigate novel teaching method assistant the classic lectures. In this paper, we introduce the multidimensional pattern in fiber-optics teaching involving theoretical and laboratory simulations. First, the theoretical simulations is demonstrated based on the self-developed software named "FB tool" which can be installed in both smart phone with Android operating system and personal computer. FB tool covers the fundamental calculations relating to transverse modes, fiber lasers and nonlinearities and so on. By comparing the calculation results with other commercial software like COMSOL, SFTool shows high accuracy with high speed. Then the laboratory simulations are designed including fiber coupling, Erbium doped fiber amplifiers, fiber components and so on. The simulations not only supports students understand basic knowledge in the course, but also provides opportunities to develop creative projects in fiber optics.

Crystal growth, characterization and theoretical studies of 4-aminopyridinium picrate

NASA Astrophysics Data System (ADS)

Aditya Prasad, A.; Muthu, K.; Rajasekar, M.; Meenatchi, V.; Meenakshisundaram, S. P.

2015-01-01

Single crystals of 4-aminopyridinium picrate (APP) were grown by slow evaporation of a mixed solvent system methanol-acetone (1:1, v/v) containing equimolar quantities of 4-aminopyridine and picric acid. Structure is elucidated by single crystal XRD analysis and the crystal belongs to monoclinic system with four molecules in the unit cell (space group P21/c) and the cell parameter values are, a = 8.513 Å (±0.015), b = 11.33 Å (±0.02), c = 14.33 Å (±0.03) and β = 104.15° (±0.019), V = 1340 A3 (±6) with refined R factors R1 = 0.0053 and wR2 = 0.0126. The electron density mapping is interpreted to find coordinates for each atom in the crystallized molecules. The various functional groups present in the molecule are confirmed by FT-IR analysis. UV-visible spectral analysis was used to determine the band gap energy of 4-aminopyridinium picrate. Powder X-ray diffraction pattern reveals the crystallinity of the as-grown crystal and it closely resembles the simulated XRD from the single crystal XRD analysis. Scanning electron microscopy reveals the surface morphology of the grown crystal. Optimized geometry is derived by Hartree-Fock theory calculations and the first-order molecular hyperpolarizability (β), theoretically calculated bond length, bond angles and excited state energy from theoretical UV-vis spectrum were estimated.

Theoretical verification of experimentally obtained conformation-dependent electronic conductance in a biphenyl molecule

NASA Astrophysics Data System (ADS)

Maiti, Santanu K.

2014-07-01

The experimentally obtained (Venkataraman et al. [1]) cosine squared relation of electronic conductance in a biphenyl molecule is verified theoretically within a tight-binding framework. Using Green's function formalism we numerically calculate two-terminal conductance as a function of relative twist angle among the molecular rings and find that the results are in good agreement with the experimental observation.

Implementation of the reduced charge state method of calculating impurity transport

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

Crume, E.C. Jr.; Arnurius, D.E.

1982-07-01

A recent review article by Hirshman and Sigmar includes expressions needed to calculate the parallel friction coefficients, the essential ingredients of the plateau-Pfirsch-Schluter transport coefficients, using the method of reduced charge states. These expressions have been collected and an expanded notation introduced in some cases to facilitate differentiation between reduced charge state and full charge state quantities. A form of the Coulomb logarithm relevant to the method of reduced charge states is introduced. This method of calculating the f/sub ij//sup ab/ has been implemented in the impurity transport simulation code IMPTAR and has resulted in an overall reduction in computationmore » time of approximately 25% for a typical simulation of impurity transport in the Impurity Study Experiment (ISX-B). Results obtained using this treatment are almost identical to those obtained using an earlier approximate theory of Hirshman.« less

Earlier Vegetation Activity Onset Enhances Springtime Water-use Efficiency in Temperate and Boreal Ecosystems

NASA Astrophysics Data System (ADS)

Jin, J.; Wang, Y.

2017-12-01

Ecosystem-scale water-use efficiency (EWUE), defined as the ratio of gross primary productivity (GPP) to evapotranspiration (ET), is an important indicator for understanding how water couples with the carbon cycle under global change. Relationships between EWUE and abiotic environmental factors (e.g. climatic factors, atmospheric CO2concentration and nitrogen deposition) have been widely investigated, but the variations in EWUE in response to biotic controls remain little understood. Here, we argue that phenology plays an important role in the regulation of EWUE by analyzing springtime EWUE responses to variability of the GPP-based vegetation activity onset (VAO) in temperate and boreal ecosystems using both satellite and flux-tower observations. Based on MODIS productions during 2000-2014, we found that spring EWUE widely significantly increased with the earlier VAO mainly in the mid- and high latitudes (over 50°N), southwestern China and mid-western North America. When AVO advanced a 10-day, the spring EWUE would increase on average by 0.17±0.09 g C kg-1 H2O in temperate and continental climates after removing the effect of environmental factors. The main response patterns of EWUE to phenology suggest that an increase in spring EWUE with an earlier VAO are mainly because the increase in GPP is relatively larger in magnitude compared to that of ET, or due to an increase in GPP accompanied by a decrease in ET, resulting from an advanced VAO. The credibility of the results is also supported by the local-scale observations. By analyzing 66 site-years of flux and meteorological data obtained from 8 temperate deciduous broadleaf forest sites across North America and Europe, spring EWUE increased 0.42±0.08 g C kg-1 H2O with a 10-day advance of VAO across all sites after controlling for environmental factors, mainly because an earlier VAO could lead to a steeper increase in GPP than in ET. Our results and conclusions highlight that phenological factors cannot be

Theoretical investigation of the breakdown electric field of SiC polymorphs

NASA Astrophysics Data System (ADS)

Yamaguchi, Kikou; Kobayashi, Daisuke; Yamamoto, Tomoyuki; Hirose, Kazuyuki

2018-03-01

The breakdown electric field of several SiC polymorphs has been investigated theoretically using a concept of "recovery rate," which is obtained by first principles calculations. A good relationship between the experimental breakdown electric fields and the calculated recovery rate of 4H-, 6H-, and 3C-SiC was obtained. In order to examine the stability of SiC polymorphs, the total electronic energies of various types of SiC crystal structures were calculated. Here, two candidates of polymorphs-GeS-type- and 2H-SiC-with energies comparable to those of experimentally well-established structures, have been obtained. The breakdown electric fields of these two polymorphs were estimated using a relationship obtained from the results of 4H-, 6H-, and 3C-SiC. This indicates that one of these polymorphs, GeS-type-SiC, has higher breakdown electric field than any other SiC polymorphs. In addition to the investigation with the recovery rate, relationship between experimental breakdown electric field and calculated band gap with recently developed accurate electron-correlation potential has been also discussed.

A theoretical and shock tube kinetic study on hydrogen abstraction from phenyl formate.

PubMed

Ning, Hongbo; Liu, Dapeng; Wu, Junjun; Ma, Liuhao; Ren, Wei; Farooq, Aamir

2018-06-12

The hydrogen abstraction reactions of phenyl formate (PF) by different radicals (H/O(3P)/OH/HO2) were theoretically investigated. We calculated the reaction energetics for PF + H/O/OH using the composite method ROCBS-QB3//M06-2X/cc-pVTZ and that for PF + HO2 at the M06-2X/cc-pVTZ level of theory. The high-pressure limit rate constants were calculated using the transition state theory in conjunction with the 1-D hindered rotor approximation and tunneling correction. Three-parameter Arrhenius expressions of rate constants were provided over the temperature range of 500-2000 K. To validate the theoretical calculations, the overall rate constants of PF + OH → Products were measured in shock tube experiments at 968-1128 K and 1.16-1.25 atm using OH laser absorption. The predicted overall rate constants agree well with the shock tube data (within 15%) over the entire experimental conditions. Rate constant analysis indicates that the H-abstraction at the formic acid site dominates the PF consumption, whereas the contribution of H-abstractions at the aromatic ring increases with temperature. Additionally, comparisons of site-specific H-abstractions from PF with methyl formate, ethyl formate, benzene, and toluene were performed to understand the effects of the aromatic ring and side-chain substituent on H-abstraction rate constants.

A first-principle calculation of the XANES spectrum of Cu2+ in water

NASA Astrophysics Data System (ADS)

La Penna, G.; Minicozzi, V.; Morante, S.; Rossi, G. C.; Stellato, F.

2015-09-01

The progress in high performance computing we are witnessing today offers the possibility of accurate electron density calculations of systems in realistic physico-chemical conditions. In this paper, we present a strategy aimed at performing a first-principle computation of the low energy part of the X-ray Absorption Spectroscopy (XAS) spectrum based on the density functional theory calculation of the electronic potential. To test its effectiveness, we apply the method to the computation of the X-ray absorption near edge structure part of the XAS spectrum in the paradigmatic, but simple case of Cu2+ in water. In order to keep into account the effect of the metal site structure fluctuations in determining the experimental signal, the theoretical spectrum is evaluated as the average over the computed spectra of a statistically significant number of simulated metal site configurations. The comparison of experimental data with theoretical calculations suggests that Cu2+ lives preferentially in a square-pyramidal geometry. The remarkable success of this approach in the interpretation of XAS data makes us optimistic about the possibility of extending the computational strategy we have outlined to the more interesting case of molecules of biological relevance bound to transition metal ions.

Intermolecular vibrational modes and H-bond interactions in crystalline urea investigated by terahertz spectroscopy and theoretical calculation

NASA Astrophysics Data System (ADS)

Zhao, Yonghong; Li, Zhi; Liu, Jianjun; Hu, Cong; Zhang, Huo; Qin, Binyi; Wu, Yifang

2018-01-01

The characteristic absorption spectra of crystalline urea in 0.6-1.8 THz region have been measured by terahertz time-domain spectroscopy at room temperature experimentally. Five broad absorption peaks were observed at 0.69, 1.08, 1.27, 1.47 and 1.64 THz respectively. Moreover, density functional theory (DFT) calculation has been performed for the isolated urea molecule, and there is no infrared intensity in the region below 1.8 THz. This means that single molecule calculations are failure to predict the experimental spectra of urea crystals. To simulate these spectra, calculations on a cluster of seven urea molecules using M06-2X and B3LYP-D3 are performed, and we found that M06-2X perform better. The observed THz vibrational modes are assigned to bending and torsional modes related to the intermolecular H-bond interactions with the help of potential energy distribution (PED) method. Using the reduced-density-gradient (RDG) analysis, the positions and types of intermolecular H-bond interactions in urea crystals are visualized. Therefore, we can confirm that terahertz spectroscopy can be used as an effective means to detect intermolecular H-bond interactions in molecular crystals.

How the Molecular Packing Affects the Room Temperature Phosphorescence in Pure Organic Compounds: Ingenious Molecular Design, Detailed Crystal Analysis, and Rational Theoretical Calculations.

PubMed

Xie, Yujun; Ge, Yuwei; Peng, Qian; Li, Conggang; Li, Qianqian; Li, Zhen

2017-05-01

Long-lived phosphorescence at room temperature (RTP) from pure organic molecules is rare. Recent research reveals various crystalline organic molecules can realize RTP with lifetimes extending to the magnitude of second. There is little research on how molecular packing affecting RTP. Three compounds are designed with similar optical properties in solution, but tremendously different solid emission characteristics. By investigating the molecular packing arrangement in single crystals, it is found that the packing style of the compact face to face favors of long phosphorescence lifetime and high photoluminescence efficiency, with the lifetime up to 748 ms observed in the crystal of CPM ((9H-carbazol-9-yl)(phenyl)methanone). Theoretical calculation analysis also reveals this kind of packing style can remarkably reduce the singlet excited energy level and prompt electron communication between dimers. Surprisingly, CPM has two very similar single crystals, labeled as CPM and CPM-A, with almost identical crystal data, and the only difference is that molecules in CPM-A crystal take a little looser packing arrangement. X-ray diffraction and cross-polarization under magic spinning 13 C NMR spectra double confirm that they are different crystals. Interestingly, CPM-A crystal shows negligible RTP compared to the CPM crystal, once again proving that the packing style is critical to the RTP property. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using MD simulations to calculate how solvents modulate solubility

PubMed Central

Liu, Shuai; Cao, Shannon; Hoang, Kevin; Young, Kayla L.; Paluch, Andrew S.; Mobley, David L.

2016-01-01

Here, our interest is in predicting solubility in general, and we focus particularly on predicting how the solubility of particular solutes is modulated by the solvent environment. Solubility in general is extremely important, both for theoretical reasons – it provides an important probe of the balance between solute-solute and solute-solvent interactions – and for more practical reasons, such as how to control the solubility of a given solute via modulation of its environment, as in process chemistry and separations. Here, we study how the change of solvent affects the solubility of a given compound. That is, we calculate relative solubilities. We use MD simulations to calculate relative solubility and compare our calculated values with experiment as well as with results from several other methods, SMD and UNIFAC, the latter of which is commonly used in chemical engineering design. We find that straightforward solubility calculations based on molecular simulations using a general small-molecule force field outperform SMD and UNIFAC both in terms of accuracy and coverage of the relevant chemical space. PMID:26878198

Theoretical investigation of the structural stabilities, optoelectronic properties and thermodynamic characteristics of GaPxSb1-x ternary alloys

NASA Astrophysics Data System (ADS)

Oumelaz, F.; Nemiri, O.; Boumaza, A.; Ghemid, S.; Meradji, H.; Bin Omran, S.; El Haj Hassan, F.; Rai, D. P.; Khenata, R.

2018-06-01

In this theoretical study, we have investigated the structural, phase transition, electronic, thermodynamic and optical properties of GaPxSb1-x ternary alloys. Our calculations are performed with the WIEN2k code based on density functional theory using the full-potential linearized augmented plane wave method. For the electron exchange-correlation potential, a generalized gradient approximation within Wu-Cohen scheme is considered. The recently developed Tran-Blaha modified Becke-Johnson potential has also been used to improve the underestimated band gap. The structural properties, including the lattice constants, the bulk moduli and their pressure derivatives are in very good agreement with the available experimental data and theoretical results. Several structural phase transitions were studied here to establish the stable structure and to predict the phase transition under hydrostatic pressure. The computed transition pressure (Pt) of the material of our interest from the zinc blende (B3) to the rock salt (B1) phase has been determined and found to agree well with the experimental and theoretical data. The calculated band structure shows that GaSb binary compound and the ternary alloys are direct band gap semiconductors. Optical parameters such as the dielectric constants and the refractive indices are calculated and analyzed. The thermodynamic results are also interpreted and analyzed.

Implementing and testing theoretical fission fragment yields in a Hauser-Feshbach statistical decay framework

NASA Astrophysics Data System (ADS)

Jaffke, Patrick; Möller, Peter; Stetcu, Ionel; Talou, Patrick; Schmitt, Christelle

2018-03-01

We implement fission fragment yields, calculated using Brownian shape-motion on a macroscopic-microscopic potential energy surface in six dimensions, into the Hauser-Feshbach statistical decay code CGMF. This combination allows us to test the impact of utilizing theoretically-calculated fission fragment yields on the subsequent prompt neutron and γ-ray emission. We draw connections between the fragment yields and the total kinetic energy TKE of the fission fragments and demonstrate that the use of calculated yields can introduce a difference in the 〈TKE〉 and, thus, the prompt neutron multiplicity v, as compared with experimental fragment yields. We deduce the uncertainty on the 〈TKE〉 and v from this procedure and identify possible applications.

Synthesis, spectroscopic and structural characterization of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine with theoretical calculations using density functional theory.

PubMed

Inkaya, Ersin; Dinçer, Muharrem; Sahan, Emine; Yıldırım, Ismail

2013-10-01

In this paper, we will report a combined experimental and theoretical investigation of the molecular structure and spectroscopic parameters (FT-IR, (1)H NMR, (13)C NMR) of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine. The compound crystallizes in the triclinic space group P-1 with Z=2. The molecular geometry was also optimized using density functional theory (DFT/B3LYP) method with the 6-311G(d,p) and 6-311++G(d,p) basis sets in ground state and compared with the experimental data. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecules has been obtained by mapping electron density isosurface with electrostatic potential (ESP). Also, non-linear optical properties of the title compound were performed at B3LYP/6-311++G(d,p) level. The theoretical results showed an excellent agreement with the experimental values. Copyright © 2013 Elsevier B.V. All rights reserved.

Theoretical calculations of high-pressure phases of NiF2: An ab initio constant-pressure study

NASA Astrophysics Data System (ADS)

Kürkçü, Cihan; Merdan, Ziya; Öztürk, Hülya

2016-12-01

We have studied the structural properties of the antiferromagnetic NiF2 tetragonal structure with P42/ mnm symmetry using density functional theory (DFT) under rapid hydrostatic pressure up to 400 GPa. For the exchange correlation energy we used the local density approximation (LDA) of Ceperley and Alder (CA). Two phase transformations are successfully observed through the simulations. The structures of XF2-type compounds crystallize in rutile-type structure. NiF2 undergoes phase transformations from the tetragonal rutile-type structure with space group P42/ mnm to orthorhombic CaCl2-type structure with space group Pnnm and from this orthorhombic phase to monoclinic structure with space group C2/ m at 152 GPa and 360 GPa, respectively. These phase changes are also studied by total energy and enthalpy calculations. According to these calculations, we perdict these phase transformations at about 1.85 and 30 GPa.

Red/blue shifting hydrogen bonds in acetonitrile-dimethyl sulphoxide solutions: FTIR and theoretical studies

NASA Astrophysics Data System (ADS)

Kannan, P. P.; Karthick, N. K.; Mahendraprabu, A.; Shanmugam, R.; Elangovan, A.; Arivazhagan, G.

2017-07-01

FTIR spectra of neat acetonitrile (AN), dimethyl sulphoxide (DMSO) and their binary solutions at various mole fractions have been recorded at room temperature. Theoretical calculations have also been carried out on acetonitrile (monomer, dimer), dimethyl sulphoxide (monomer, dimer) and AN - DMSO complex molecules. 1:2 (AN:DMSO) and 2:1 complexation through the red shifting (AN) C - H ⋯ O = S(DMSO) and blue shifting (DMSO) C - H ⋯ N ≡ C(AN) hydrogen bonds has been identified. The experimental and theoretical studies favour the presence of both the monomer and dimer in liquid AN, but only closed dimers in DMSO. The dipole-dipole interactions existed in AN and DMSO dimers disappear in the complex molecules. Partial π bond between S and O atoms, and three lone pair of electrons on oxygen atom of DMSO have been noticed theoretically.

a New Method for Calculating the Fractal Dimension of Surface Topography

NASA Astrophysics Data System (ADS)

Zuo, Xue; Zhu, Hua; Zhou, Yuankai; Li, Yan

2015-06-01

A new method termed as three-dimensional root-mean-square (3D-RMS) method, is proposed to calculate the fractal dimension (FD) of machined surfaces. The measure of this method is the root-mean-square value of surface data, and the scale is the side length of square in the projection plane. In order to evaluate the calculation accuracy of the proposed method, the isotropic surfaces with deterministic FD are generated based on the fractional Brownian function and Weierstrass-Mandelbrot (WM) fractal function, and two kinds of anisotropic surfaces are generated by stretching or rotating a WM fractal curve. Their FDs are estimated by the proposed method, as well as differential boxing-counting (DBC) method, triangular prism surface area (TPSA) method and variation method (VM). The results show that the 3D-RMS method performs better than the other methods with a lower relative error for both isotropic and anisotropic surfaces, especially for the surfaces with dimensions higher than 2.5, since the relative error between the estimated value and its theoretical value decreases with theoretical FD. Finally, the electrodeposited surface, end-turning surface and grinding surface are chosen as examples to illustrate the application of 3D-RMS method on the real machined surfaces. This method gives a new way to accurately calculate the FD from the surface topographic data.

Do BRCA1/2 mutation carriers have an earlier onset of natural menopause?

PubMed

van Tilborg, Theodora C; Broekmans, Frank J; Pijpe, Anouk; Schrijver, Lieske H; Mooij, Thea M; Oosterwijk, Jan C; Verhoef, Senno; Gómez Garcia, Encarna B; van Zelst-Stams, Wendy A; Adank, Muriel A; van Asperen, Christi J; van Doorn, Helena C; van Os, Theo A; Bos, Anna M; Rookus, Matti A; Ausems, Margreet G

2016-08-01

It has been hypothesized that BRCA1/2 mutation carriers have an earlier age at natural menopause (ANM), although to date findings are inconclusive. This study assessed the influence of BRCA mutation status on ANM, and aimed to explore the reasons of inconsistency in the literature. Cross-sectional assessment from an ongoing nationwide cohort study among members of BRCA1/2 mutated families. Information was obtained by a standardized questionnaire. Kaplan-Meier curves were constructed, and Cox regression was used to assess the association between BRCA1/2 mutation status and ANM. Adjustments were made for birth cohort, family, smoking, use of hormonal contraceptives, and parity. A total of 1,208 BRCA1/2 mutation carriers and 2,211 proven noncarriers were included. Overall, no association was found between BRCA1/2 mutation status and ANM (adjusted hazard ratio [HR] = 1.06 [95% CI, 0.87-1.30]). We examined if the null finding was due to informative censoring by uptake of risk-reducing salpingo-oophorectomy. Indeed, within the oldest birth cohort, in which the percentage of surgical menopause events was lowest and comparable between carriers and noncarriers, the HR for earlier natural menopause in carriers was 1.45 (95% CI, 1.09-1.94). The second oldest birth cohort, however, demonstrated a decreased HR (0.67 [95% CI, 0.46-0.98]), and thus no trend over birth cohorts was found. Various types of selection bias hamper the comparison of ANM between BRCA1/2 mutation carriers and noncarriers, genetically tested in the clinic.

Earlier parental set bedtimes as a protective factor against depression and suicidal ideation.

PubMed

Gangwisch, James E; Babiss, Lindsay A; Malaspina, Dolores; Turner, J Blake; Zammit, Gary K; Posner, Kelly

2010-01-01

To examine the relationships between parental set bedtimes, sleep duration, and depression as a quasi-experiment to explore the potentially bidirectional relationship between short sleep duration and depression. Short sleep duration has been shown to precede depression, but this could be explained as a prodromal symptom of depression. Depression in an adolescent can affect his/her chosen bedtime, but it is less likely to affect a parent's chosen set bedtime which can establish a relatively stable upper limit that can directly affect sleep duration. Multivariate cross-sectional analyses of the ADD Health using logistic regression. United States nationally representative, school-based, probability-based sample in 1994-96. Adolescents (n = 15,659) in grades 7 to 12. Adolescents with parental set bedtimes of midnight or later were 24% more likely to suffer from depression (OR = 1.24, 95% CI 1.04-1.49) and 20% more likely to have suicidal ideation (1.20, 1.01-1.41) than adolescents with parental set bedtimes of 10:00 PM or earlier, after controlling for covariates. Consistent with sleep duration and perception of getting enough sleep acting as mediators, the inclusion of these variables in the multivariate models appreciably attenuated the associations for depression (1.07, 0.88-1.30) and suicidal ideation (1.09, 0.92-1.29). The results from this study provide new evidence to strengthen the argument that short sleep duration could play a role in the etiology of depression. Earlier parental set bedtimes could therefore be protective against adolescent depression and suicidal ideation by lengthening sleep duration.

Seeking potential anticonvulsant agents that target GABAA receptors using experimental and theoretical procedures

NASA Astrophysics Data System (ADS)

Saavedra-Vélez, Margarita Virginia; Correa-Basurto, José; Matus, Myrna H.; Gasca-Pérez, Eloy; Bello, Martiniano; Cuevas-Hernández, Roberto; García-Rodríguez, Rosa Virginia; Trujillo-Ferrara, José; Ramos-Morales, Fernando Rafael

2014-12-01

The aim of this study was to identify compounds that possess anticonvulsant activity by using a pentylenetetrazol (PTZ)-induced seizure model. Theoretical studies of a set of ligands, explored the binding affinities of the ligands for the GABAA receptor (GABAAR), including some benzodiazepines. The ligands satisfy the Lipinski rules and contain a pharmacophore core that has been previously reported to be a GABAAR activator. To select the ligands with the best physicochemical properties, all of the compounds were analyzed by quantum mechanics and the energies of the highest occupied molecular orbital and lowest unoccupied molecular orbital were determined. Docking calculations between the ligands and the GABAAR were used to identify the complexes with the highest Gibbs binding energies. The identified compound D1 (dibenzo( b,f)(1,4)diazocine-6,11(5H,12H)-dione) was synthesized, experimentally tested, and the GABAAR-D1 complex was submitted to 12-ns-long molecular dynamics (MD) simulations to corroborate the binding conformation obtained by docking techniques. MD simulations were also used to analyze the decomposition of the Gibbs binding energy of the residues involved in the stabilization of the complex. To validate our theoretical results, molecular docking and MD simulations were also performed for three reference compounds that are currently in commercial use: clonazepam (CLZ), zolpidem and eszopiclone. The theoretical results show that the GABAAR-D1, and GABAAR-CLZ complexes bind to the benzodiazepine binding site, share a similar map of binding residues, and have similar Gibbs binding energies and entropic components. Experimental studies using a PTZ-induced seizure model showed that D1 possesses similar activity to CLZ, which corroborates the predicted binding free energy identified by theoretical calculations.

Solution and solid-state effects on NMR chemical shifts in sesquiterpene lactones: NMR, X-ray, and theoretical methods.

PubMed

Dračínský, Martin; Buděšínský, Miloš; Warżajtis, Beata; Rychlewska, Urszula

2012-01-12

Selected guaianolide type sesquiterpene lactones were studied combining solution and solid-state NMR spectroscopy with theoretical calculations of the chemical shifts in both environments and with the X-ray data. The experimental (1)H and (13)C chemical shifts in solution were successfully reproduced by theoretical calculations (with the GIAO method and DFT B3LYP 6-31++G**) after geometry optimization (DFT B3LYP 6-31 G**) in vacuum. The GIPAW method was used for calculations of solid-state (13)C chemical shifts. The studied cases involved two polymorphs of helenalin, two pseudopolymorphs of 6α-hydroxydihydro-aromaticin and two cases of multiple asymmetric units in crystals: one in which the symmetry-independent molecules were connected by a series of hydrogen bonds (geigerinin) and the other in which the symmetry-independent molecules, deprived of any specific intermolecular interactions, differed in the conformation of the side chain (badkhysin). Geometrically different molecules present in the crystal lattices could be easily distinguished in the solid-state NMR spectra. Moreover, the experimental differences in the (13)C chemical shifts corresponding to nuclei in different polymorphs or in geometrically different molecules were nicely reproduced with the GIPAW calculations.

Theoretical results on the tandem junction solar cell based on its Ebers-Moll transistor model

NASA Technical Reports Server (NTRS)

Goradia, C.; Vaughn, J.; Baraona, C. R.

1980-01-01

A one-dimensional theoretical model of the tandem junction solar cell (TJC) with base resistivity greater than about 1 ohm-cm and under low level injection has been derived. This model extends a previously published conceptual model which treats the TJC as an npn transistor. The model gives theoretical expressions for each of the Ebers-Moll type currents of the illuminated TJC and allows for the calculation of the spectral response, I(sc), V(oc), FF and eta under variation of one or more of the geometrical and material parameters and 1MeV electron fluence. Results of computer calculations based on this model are presented and discussed. These results indicate that for space applications, both a high beginning of life efficiency, greater than 15% AM0, and a high radiation tolerance can be achieved only with thin (less than 50 microns) TJC's with high base resistivity (greater than 10 ohm-cm).

Comparisons of laboratory wavelength measurements with theoretical calculations for neon-like through lithium-like argon, sulfur, and silicon

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

Lepson, J K; Beiersdorfer, P; Behar, E

Atomic structure codes have a difficult time accurately calculating the wavelengths of many-electron ions without the benefit of laboratory measurements. This is especially true for wavelengths of lines in the extreme ultraviolet and soft x-ray regions. We are using the low-energy capability of the Livermore electron beam ion traps to compile a comprehensive catalog of astrophysically relevant emission lines in support of satellite x-ray observations. Our database includes wavelength measurements, relative intensities, and line assignments, and is compared to a full set of calculations using the Hebrew University - Lawrence Livermore Atomic Code (HULLAC). Mean deviation of HULLAC calculations frommore » our measured wavelength values is highest for L-shell transitions of neon-like ions and lowest for lithium-like ions, ranging from a mean deviation of over 0.5 {angstrom} for Si V to 12 m{angstrom} in Ar XVI.« less

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

NASA Technical Reports Server (NTRS)

Eggleston, John M; Diederich, Franklin W

1957-01-01

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

On the importance of full-dimensionality in low-energy molecular scattering calculations

PubMed Central

Faure, Alexandre; Jankowski, Piotr; Stoecklin, Thierry; Szalewicz, Krzysztof