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At least 577 records · Page 32

Computing Reaction Kinetics with MC-PDFT–OPESf: Combining Multireference Electronic Structure Theory and Enhanced Sampling

Accurate rate constants are crucial for understanding and optimizing catalytic reactions mediated by enzymes, metalloproteins, and heterogeneous catalysts. These systems frequently present a dual computational challenge. Multiconfigurational reaction sites require multireference techniques for the accurate treatment of the electronic structure, and high activation barriers prevent efficient sampling of unbiased reactive transitions. In this work, we combine multiconfiguration pair-density functional theory (MC-PDFT) as an accurate and efficient multireference electronic structure method with on-the-fly probability-enhanced sampling flooding (OPESf) as an enhanced sampling method capable of accelerating reactive transitions. We demonstrate the approach on the Diels–Alder [4+2] cycloaddition between cis-butadiene and ethene as a reaction characterized by a large activation barrier and multireference character. MC-PDFT–OPESf provides reaction rates in agreement with experiments at a fraction of the computational cost required by conventional unbiased ab initio calculations. Here, we propose MC-PDFT–OPESf as an efficient approach for computing kinetics in strongly correlated molecular systems.

Chemical calculations↗

Computational methods for probability of instability calculations

This paper summarizes the development of the methods and a computer program to compute the probability of instability of a dynamic system than can be represented by a system of second-order ordinary linear differential equations. Two instability criteria based upon the roots of the characteristics equation or Routh-Hurwitz test functions are investigated. Computational methods based on system reliability analysis methods and importance sampling concepts are proposed to perform efficient probabilistic analysis. Numerical examples are provided to demonstrate the methods.

Wu, Y.-T.↗

Front Delineation and Tracking with Multiple Underwater Vehicles

This work describes a method for detecting and tracking ocean fronts using multiple autonomous underwater vehicles. Multiple vehicles — equally-spaced along the expected frontal boundary — complete near parallel transects orthogonal to the front. Lateral gradients are used to determine the location of the front crossing from each individual vehicle transect by detecting a change in the observed water property. Adaptive control of the vehicles ensure they remain perpendicular to the estimated front boundary as it evolves over time. This method was demonstrated in and around Monterey Bay, California in May of 2017. We compare the front detection method to previously used methods. We introduce a metric in order to evaluate the adaptive control techniques presented. We show the capability of this method for repeated sampling across a dynamic two-dimensional ocean front using short-range Iver AUVs. This method extends to tracking gradients of different properties using a variety of vehicles.

Chavez, Francisco P.↗

Measurement of Seebeck coefficient using a large thermal gradient

The integral method of measuring the Seebeck voltage, V(T), has been applied to short rod-shaped samples. In the present method, one end of the sample is held at a fixed temperature and the other end is automatically varied through a temperature T range of interest, up to a maximum temperature of 1000 C. The Seebeck coefficient is then obtained from the slope of the V(T) vs T curve. The method offers simplicity of sample handling and minimal operator involvement.

Wood, C.↗

Dividing the Concentrator Target From the Genesis Mission

The Genesis spacecraft, launched in 2001, traveled to a Lagrangian point between the Earth and Sun to collect particles from the solar wind and return them to Earth. However, during the return of the spacecraft in 2004, the parachute failed to open during descent, and the Genesis spacecraft crashed into the Utah desert. Many of the solar wind collectors were broken into smaller pieces, and the field team rapidly collected the capsule and collector pieces for later assessment. On each of the next few days, the team discovered that various collectors had survived intact, including three of four concentrator targets. Within a month, the team had imaged more than 10,000 fragments and packed them for transport to the Astromaterials Acquisition and Curation Office within the ARES Directorate at JSC. Currently, the Genesis samples are curated along with the other extraterrestrial sample collections within ARES. Although they were broken and dirty, the Genesis solar wind collectors still offered the science community the opportunity to better understand our Sun and the solar system as a whole. One of the more highly prized concentrator collectors survived the crash almost completely intact. The Genesis Concentrator was designed to concentrate the solar wind by a factor of at least 20 so that solar oxygen and nitrogen isotopes could be measured. One of these materials was the Diamond-on-Silicon (DoS) concentrator target. Unfortunately, the DoS concentrator broke on impact. Nevertheless, the scientific value of the DoS concentrator target was high. The Genesis Allocation Committee received a request for approximately 1 cm(sup 2) of the DoS specimen taken near the focal point of the concentrator for the analysis of solar wind nitrogen isotopes. The largest fragment, Genesis sample 60000, was designated for this allocation and needed to be precisely cut. The requirement was to subdivide the designated sample in a manner that prevented contamination of the sample and minimized the risk of losing or breaking the precious requested sample fragment. The Genesis curator determined that the use of laser scribing techniques to "cut" a precise line and subsequently cleave the sample (in a controlled break of the sample along that line) was the best method for accomplishing the sample subdivision. However, there were risks, including excess heating of the sample, that could cause some of the implanted solar wind to be lost via thermal diffusion. Accidentally breaking the sample during the handling and cleaving process was an additional risk. Early in fiscal year 2013, to address this delicate, complicated task, the ARES Directorate assembled its top scientists to develop a cutting plan that would ensure success when applied to the actual concentrator target wafer; i.e., to produce an approximately 1 cm(sup 2) piece from the requested area of the wafer. The team, subsequently referred to as the JSC Genesis Tiger Team, spent months researching and testing parameters and techniques related to scribing, cleaving, transporting, handling, and holding (i.e., mounting) the specimen. The investigation required considerable "thinking outside the box," and many, many trials using nonflight wafer analogs. After all preliminary testing, the following method was adopted as the final cutting plan. It was used in two final end-to-end practice runs before being used on the actual flight target wafer. The wafer was oriented on the laser cutting stage with the 100 and 010 directions of the wafer parallel to the corresponding X and Y directions of the cutting stage. The laser was programed to scribe 31 lines of the appropriate length along the Y stage direction. The programed scribe lines were separated by 5 micron in the X direction. The laser parameters were set as follows: (1) The laser power was 0.5 watts; (2) each line consisted of 50 passes, with the Z position being advanced 5 micron per pass; and (3) 30 s would elapse before the next line was scribed to allow for wafer cool down from any possible heating via the laser. The ablated material that "stuck" in the "scribe-cut" was removed from the "cut" using an ultrasonic micro-tool. After all the ablated silicon was removed from the wafer, the wafer was repositioned in exactly the same orientation on the laser stage. The laser was focused using the bottom of the wafer channel, and the 31-line scribing pattern described above was reprogrammed using the Z position of the groove bottom as the starting Z value instead of the top wafer surface, which was used previously. Upon completion of the second set of scribes, the ultrasonic micro-tool was again used to clean out the cut. The wafer was remounted on the stage in exactly the same orientation as before. The laser was again focused on the bottom of the groove. This time, however, the laser was.programed to scribe only one line down the exact center of the channel. The final scribe line consisted of 100 passes with a Z advance of 5 micron per pass and with the laser power set at 0.5 watts. As mentioned above, the final cutting plan was practiced in two end-to-end trials using non-flight, triangular-shaped silicon wafers similar in size and orientation to the actual DOS 60000 target sample. The actual scribing of the triangular-shaped wafers required scribing two lines and cleaving (i.e. scribe-cleave, then scribe-cleave) to obtain the piece requested for allocation. Early in December 2012, after many months of experiments and practicing and perfecting the techniques and procedures, the team successfully subdivided the Genesis DoS 60000 target sample, one of the most scientifically important samples from the Genesis mission (figure 2). On December 17, 2012, the allocated piece of concentrator target sample was delivered to the requesting principal investigator.The cutting plan developed for the subdivision of this sample will be used as the model for subdividing future requested Genesis flight wafers (appropriately modified for different wafer types).

Lauer, H. V., Jr.↗

Calculation of power spectrums from digital time series with missing data points

Two algorithms are developed for calculating power spectrums from the autocorrelation function when there are missing data points in the time series. Both methods use an average sampling interval to compute lagged products. One method, the correlation function power spectrum, takes the discrete Fourier transform of the lagged products directly to obtain the spectrum, while the other, the modified Blackman-Tukey power spectrum, takes the Fourier transform of the mean lagged products. Both techniques require fewer calculations than other procedures since only 50% to 80% of the maximum lags need be calculated. The algorithms are compared with the Fourier transform power spectrum and two least squares procedures (all for an arbitrary data spacing). Examples are given showing recovery of frequency components from simulated periodic data where portions of the time series are missing and random noise has been added to both the time points and to values of the function. In addition the methods are compared using real data. All procedures performed equally well in detecting periodicities in the data.

Murray, C. W., Jr.↗

Efficient sampling of free energy landscapes with functions in Sobolev spaces

Molecular simulations of biological and physical phenomena generally involve sampling complicated, rough energy landscapes characterized by multiple local minima. In this work, we introduce a new family of methods for advanced sampling that draw inspiration from functional representations used in machine learning and approximation theory. As shown here, such representations are particularly well suited for learning free energies using artificial neural networks. As a system evolves through phase space, the proposed methods gradually build a model for the free energy as a function of one or more collective variables, from both the frequency of visits to distinct states and generalized force estimates corresponding to such states. Implementation of the methods is relatively simple and, more importantly, for the representative examples considered in this work, they provide computational efficiency gains of up to several orders of magnitude over other widely used simulation techniques.

Approximation theory↗

Computational Optimization of 133m Xe Production via Neutron Irradiation in a TRIGA Reactor

Here, the Comprehensive Nuclear-Test-Ban Treaty bans all nuclear tests worldwide. As part of treaty compliance, the concentration of radioactive nuclides in the atmosphere is monitored to detect nuclear weapons tests. Radioactive noble gas fission products, specifically radioxenon, can vent into the atmosphere after a nuclear weapons test, even if the test is well contained underground or underwater. Radioxenon thus serves as a signal for nuclear weapons tests. All atmospheric monitoring systems require samples of radioxenon isotopes for detector calibration, quality control, and certification. Here, we present a novel, improved method for creating samples of 133m Xe via neutron irradiation of 132 Xe in the Washington State University TRIGA reactor. 132 Xe neutron absorption results in either 133 Xe or 133m Xe—thermal neutron absorption results in 133m Xe 12% of the time, while fast neutron absorption (above ~1 MeV) results in 133m Xe ~50% of the time. To optimize the production of 133m Xe via neutron absorption in 132 Xe in the thermal TRIGA reactor, spectral tuning using an irradiation chamber is required to maximize the fraction of fast neutrons being absorbed and minimize the number of thermal neutrons interacting with the 132 Xe. We used MCNP to tally 132 Xe absorptions with the isotopic tally function, flux tallies and neutron attenuation to estimate the number of neutrons reaching the 132 Xe through the irradiation chamber, and the adjoint importance function to improve the source strength estimate. Additionally, we performed a heat transfer analysis for safety considerations. It was determined that the use of a 96% enriched 10 B boron carbide chamber, placed next to the fuel elements in reactor position D8, increases the 133m Xe/ 133 Xe activity ratio from a baseline value of 0.3 to 1.0, a 233% increase. Additionally, it was determined that the alpha heating produced in the boron does not become an unmanageable problem in the Washington State University reactor.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

Mahaffy, P.↗

Numerical Experiment with Time and Spatial Accuracy of Navier-Stokes Computation For Helicopter Problems

Helicopter flowfields are highly unsteady, nonlinear and three-dimensional. In forward flight and in hover, the rotor blades interact with the tip vortex and wake sheet developed by either itself or the other blades. This interaction, known as blade-vortex interactions (BVI), results in unsteady loading of the blades and can cause a distinctive acoustic signature. Accurate and cost-effective computational fluid dynamic solutions that capture blade-vortex interactions can help rotor designers and engineers to predict rotor performance and to develop designs for low acoustic signature. Such a predictive method must preserve a blade's shed vortex for several blade revolutions before being dissipated. A number of researchers have explored the requirements for this task. This paper will outline some new capabilities that have been added to the NASA Ames' OVERFLOW code to improve its overall accuracy for both vortex capturing and unsteady flows. To highlight these improvements, a number of case studies will be presented. These case studies consist of free convection of a 2-dimensional vortex, dynamically pitching 2-D airfoil including light-stall, and a full 3-D unsteady viscous solution of a helicopter rotor in forward flight In this study both central and upwind difference schemes are modified to be more accurate. Central difference scheme is chosen for this simulation because the flowfield is not dominated by strong shocks. The feature of shock-vortex interaction in such a flow is less important than the dominant blade-vortex interaction. The scheme is second-order accurate in time and solves the thin-layer Navier-Stokes equations in fully-implicit manner at each time-step. The spatial accuracy is either second and fourth-order central difference or third-order upwind difference using Roe-flux and MUSCLE scheme. This paper will highlight and demonstrate the methods for several sample cases and for a helicopter rotor. Preliminary computations on a rotor were performed by using this method and are in the process of documentation.

Ahmad, Jasim↗

Sample processor for the automatic extraction of families of compounds from liquid samples and/or homogenized solid samples suspended in a liquid

A sample processor and method for the automatic extraction of families of compounds, known as extracts, from liquid and/or homogenized solid samples are disclosed. The sample processor includes a tube support structure which supports a plurality of extraction tubes, each containing a sample from which families of compounds are to be extracted. The support structure is moveable automatically with respect to one or more extraction stations, so that as each tube is at each station a solvent system, consisting of a solvent and reagents, is introduced therein. As a result an extract is automatically extracted from the tube. The sample processor includes an arrangement for directing the different extracts from each tube to different containers, or to direct similar extracts from different tubes to the same utilization device.

Jahnsen, Vilhelm J.↗

Assessing Risk Due to Small Sample Size in Probability of Detection Analysis Using Tolerance Intervals

Small sample size (e.g.6-30) poses risk in results of probability of detection (POD) analysis using tolerance intervals. This method is also called as the limited sample or LS POD. The analysis is performed either during NDE procedure qualification or for assessment of reliability of an NDE procedure. The risk is primarily due to sampling error. Smaller samples are not likely to be random to the population or representative of the population. The small samples are likely to be biased. Biased samples have smaller standard deviation compared to the population. POD analysis with small biased sample can lead to overestimation of POD. Many sampling schemes are available in statistics to mitigate sampling risk. Primary objective of POD analysis is to determine a decision threshold from signal response measurements of a sample such that it is less than or equal to population decision threshold for 90% POD. Sampling error implies that this NDE reliability condition is violated. One of sampling types is called a representative sample. Representative samples reduce variance in POD estimates but also reduce magnitude of the error. Sampling sensitivity analysis for some sampling types is performed here using repetitive random sampling or Monte Carlo method. Six sampling types are considered for comparison. Some of the sampling types are similar to drawing a representative sample. LS POD model assumes random sampling. Therefore, random sampling is used as a basis for comparison with each sampling type. The sampling types used in the analysis are, A. Nominal and worst-case sampling, B. Worst-case sampling, C. Nominal case sampling, D. Random sampling, E. Random target, and sub-target sampling. F. Nominal target and sub-target sampling. Results of Monte Carlo simulation indicate that type F sampling can mitigate sampling risk and is also more practical to implement. Type A sampling may also mitigate the sampling risk, but it may be less practical to implement.

Ajay M Koshti↗

Determination of Silicon in Hydrazine

Inductively coupled plasma-mass spectrometry (ICP-MS) is a highly sensitive technique sometimes used for the trace determination of silicon at a mass-to-charge (m/z) ratio of 28, the most abundant natural isotope of silicon. Unfortunately, ICP-MS is unable to differentiate between other sources of m/z 28 and false positive results for silicon will result when other sources of m/z 28 are present. Nitrogen was a major source of m/z 28 and contributes to the m/z 28 signal when hydrazine sample or nitric acid preservative is introduced into the plasma. Accordingly, this work was performed to develop a sample preparation step coupled with an ICP-MS analysis that minimized non-silicon sources of m/z 28. In the preparatory step of this method, the hydrazine sample was first decomposed predominately to nitrogen gas and water with copper-catalyzed hydrogen peroxide. In the analysis step, ICP-MS was used without nitric acid preservative in samples or standards. Glass, a potential source of silicon contamination, was also avoided where possible. The method was sensitive, accurate, and reliable for the determination of silicon in monopropellant grade hydrazine (MPH) in AF-E-332 elastomer leaching tests. Results for silicon in MPH were comparable to those reported in the literature for other studies.

McClure, Mark B.↗

Climatic Analysis of Oceanic Water Vapor Transports Based on Satellite E-P Datasets

Understanding the climatically varying properties of water vapor transports from a robust observational perspective is an essential step in calibrating climate models. This is tantamount to measuring year-to-year changes of monthly- or seasonally-averaged, divergent water vapor transport distributions. This cannot be done effectively with conventional radiosonde data over ocean regions where sounding data are generally sparse. This talk describes how a methodology designed to derive atmospheric water vapor transports over the world oceans from satellite-retrieved precipitation (P) and evaporation (E) datasets circumvents the problem of inadequate sampling. Ultimately, the method is intended to take advantage of the relatively complete and consistent coverage, as well as continuity in sampling, associated with E and P datasets obtained from satellite measurements. Independent P and E retrievals from Special Sensor Microwave Imager (SSM/I) measurements, along with P retrievals from Tropical Rainfall Measuring Mission (TRMM) measurements, are used to obtain transports by solving a potential function for the divergence of water vapor transport as balanced by large scale E - P conditions.

Smith, Eric A.↗

A Review of Online Monitoring within Used Nuclear Fuel Recycling Processes

The processing of used nuclear fuels and related materials is often complex and variable. The ability to quickly optimize conditions to the material being processed can aid in increasing efficiency and safety, but requires very quick determination of the conditions present in the feedstock, the process, and the product. Furthermore, accurate quantification of materials such as enriched uranium and plutonium aids in maintaining material accountancy and avoiding nuclear proliferation risks. Traditional analytical methods require process samples to be collected and analyzed in a laboratory, which often takes days to weeks. Online monitoring is suitable for collecting this information nearly instantaneously, enabling much faster optimization of the process or detection of material diversion. Online monitoring is also beneficial as it is typically based on robust and nondestructive analytical methods, so no material is removed as samples. This review examines online monitoring relevant to used nuclear fuel processing for the determination of both chemical and physical parameters. The chemical parameters include quantities such as concentration, isotopic composition, and speciation. These values are often well suited to spectroscopic or spectrometric measurements as they are fast, nondestructive, and easily implemented in an online manner. Physical quantities are often more varied and include temperature, pressure, tank fill levels, and others. Due to the specificity of these quantities, specialized instrumentation is often used. However, this instrumentation is often amendable to online monitoring.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Dynamic control modification techniques in teleoperation of a flexible manipulator

The objective of this research is to reduce the end-point vibration of a large, teleoperated manipulator while preserving the usefulness of the system motion. A master arm is designed to measure desired joint angles as the user specifies a desired tip motion. The desired joint angles from the master arm are the inputs to an adaptive PD control algorithm that positions the end-point of the manipulator. As the user moves the tip of the master, the robot will vibrate at its natural frequencies which makes it difficult to position the end-point. To eliminate the tip vibration during teleoperated motions, an input shaping method is presented. The input shaping method transforms each sample of the desired input into a new set of impulses that do not excite the system resonances. The method is explained using the equation of motion for a simple, second-order system. The impulse response of such a system is derived and the constraint equations for vibrationless motion are presented. To evaluate the robustness of the method, a different residual vibration equation from Singer's is derived that more accurately represents the input shaping technique. The input shaping method is shown to actually increase the residual vibration in certain situations when the system parameters are not accurately specified. Finally, the implementation of the input shaping method to a system with varying parameters is shown to induce a vibration into the system. To eliminate this vibration, a modified command shaping technique is developed. The ability of the modified command shaping method to reduce vibration at the system resonances is tested by varying input perturbations to trajectories in a range of possible user inputs. By comparing the frequency responses of the transverse acceleration at the end-point of the manipulator, the modified method is compared to the original PD routine. The control scheme that produces the smaller magnitude of resonant vibration at the first natural frequency is considered the more effective control method.

Magee, David Patrick↗

Determination of design and operation parameters for upper atmospheric research instrumentation to yield optimum resolution with deconvolution, appendix 3

The Always-Convergent Iterative Noise Removal and Deconvolution Method of Ioup is applied as a single-filter in the transform domain to deconvolution with both narrow and wide Gaussian impulse response functions. The wraparound error for both cases is also studied. A method is developed by which one can find the optimum iteration number for single-filter iterative deconvolution of sampled data. The method employs the mean square error (MSE), the square of the difference between the deconvolved result and the input, for optimization. The MSE decreases as the deconvolution iterations proceed, but at the optimum iteration number, the MSE starts to increase. This procedure is repeated for signal-to-noise ratio of 10 to 150. The optimum iteration number and the MSE are plotted vs SNR. By knowing the SNR for a particular experiment, one can find the optimum iteration number and MSE.

Ioup, George E.↗