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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,711 records · Page 95
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Line Ratios for Solar Wind Charge Exchange with Comets

Charge exchange (CX) has emerged in X-ray emission modeling as a significant process that must be considered in many astrophysical environments—particularly comets. Comets host an interaction between solar wind ions and cometary neutrals to promote solar wind charge exchange (SWCX). X-ray observatories provide astronomers and astrophysicists with data for many X-ray emitting comets that are impossible to accurately model without reliable CX data. Here, we utilize a streamlined set of computer programs that incorporate the multi-channel Landau–Zener theory and a cascade model for X-ray emission to generate cross sections and X-ray line ratios for a variety of bare and non-bare ion single electron capture (SEC) collisions. Namely, we consider collisions between the solar wind constituent bare and H-like ions of C, N, O, Ne, Na, Mg, Al, and Si and the cometary neutrals H{sub 2}O, CO, CO{sub 2}, OH, and O. To exemplify the application of this data, we model the X-ray emission of Comet C/2000 WM1 (linear) using the CX package in SPEX and find excellent agreement with observations made with the XMM-Newton RGS detector. Our analyses show that the X-ray intensity is dominated by SWCX with H, while H{sub 2}O plays a secondary role. This is the first time, to our knowledge, that CX cross sections have been implemented into a X-ray spectral fitting package to determine the H to H{sub 2}O ratio in cometary atmospheres. The CX data sets are incorporated into the modeling packages SPEX and Kronos .

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1992

Mean free paths of energetic particles at very large heliodistances (Pioneer 11 at 20 AU)

The parallel mean free path and the diffusion coefficient parallel to the magnetic field line are derived from magnetic field data at 20 AU to characterize heliospheric modulation and energetic-particle/magnetic-field interaction. The computational method of Moussas et al. (1975, 1982) is employed, and the values of the parallel mean free path are shown to be significantly larger than the values estimated in studies of up to 6 AU. The distance dependence of the parallel diffusion mean free path is found to follow a power law, and the diffusion coefficient dependence upon energy is determined by a constant mean free path and the velocity of the particle. The contribution of the diffusion coefficient perpendicular to the magnetic field is expected to dominate the radial diffusion coefficient of cosmic rays, although the contribution of the diffusion parallel to the field is important with respect to the small-scale structure of intensity gradients.

Moussas, X.↗
DOE OSTI2015

Exploiting data representation for fault tolerance

Incorrect computer hardware behavior may corrupt intermediate computations in numerical algorithms, possibly resulting in incorrect answers. Prior work models misbehaving hardware by randomly flipping bits in memory. We start by accepting this premise, and present an analytic model for the error introduced by a bit flip in an IEEE 754 floating-point number. We then relate this finding to the linear algebra concepts of normalization and matrix equilibration. In particular, we present a case study illustrating that normalizing both vector inputs of a dot product minimizes the probability of a single bit flip causing a large error in the dot product's result. Moreover, the absolute error is either less than one or very large, which allows detection of large errors. Then, we apply this to the GMRES iterative solver. We count all possible errors that can be introduced through faults in arithmetic in the computationally intensive orthogonalization phase of GMRES, and show that when the matrix is equilibrated, the absolute error is bounded above by one.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2010

Clinical application and validation of an iterative forward projection matching algorithm for permanent brachytherapy seed localization from conebeam-CT x-ray projections

Purpose: To experimentally validate a new algorithm for reconstructing the 3D positions of implanted brachytherapy seeds from postoperatively acquired 2D conebeam-CT (CBCT) projection images. Methods: The iterative forward projection matching (IFPM) algorithm finds the 3D seed geometry that minimizes the sum of the squared intensity differences between computed projections of an initial estimate of the seed configuration and radiographic projections of the implant. In-house machined phantoms, containing arrays of 12 and 72 seeds, respectively, are used to validate this method. Also, four {sup 103}Pd postimplant patients are scanned using an ACUITY digital simulator. Three to ten x-ray images are selected from the CBCT projection set and processed to create binary seed-only images. To quantify IFPM accuracy, the reconstructed seed positions are forward projected and overlaid on the measured seed images to find the nearest-neighbor distance between measured and computed seed positions for each image pair. Also, the estimated 3D seed coordinates are compared to known seed positions in the phantom and clinically obtained VariSeed planning coordinates for the patient data. Results: For the phantom study, seed localization error is (0.58{+-}0.33) mm. For all four patient cases, the mean registration error is better than 1 mm while compared against the measured seed projections. IFPM converges in 20-28 iterations, with a computation time of about 1.9-2.8 min/iteration on a 1 GHz processor. Conclusions: The IFPM algorithm avoids the need to match corresponding seeds in each projection as required by standard back-projection methods. The authors' results demonstrate {approx}1 mm accuracy in reconstructing the 3D positions of brachytherapy seeds from the measured 2D projections. This algorithm also successfully localizes overlapping clustered and highly migrated seeds in the implant.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2017

New estimates of extensive-air-shower energies on the basis of signals in scintillation detectors

New formulas for estimating the energy of inclined extensive air showers (EASs) on the basis of signals in detectors by means of an original method and detailed tables of signals induced in scintillation detectors by photons, electrons, positrons, and muons and calculated with the aid of the GEANT4 code package were proposed in terms of the QGSJETII-04, EPOS LHC, and GHEISHA models. The parameters appearing in the proposed formulas were calculated by employing the CORSIKA code package. It is shown that, for showers of zenith angles in the range of 20◦–45◦, the standard constant-intensity-cut method, which is used to interpret data from the Yakutsk EAS array, overestimates the shower energy by a factor of 1.2 to 1.5. It is proposed to employ the calculated VEM (Vertical Equivalent Muon) signal units of 10.8 and 11.4 MeV for, respectively, ground-based and underground scintillation detectors and to take into account the dependence of signals on the azimuthal angle of the detector position and fluctuations in the development of showers.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS1976

Pressure and velocity in a developing coaxial jet

Determinations of static pressure, mean velocity and turbulence intensity in the developing region of coaxial jets are presented. Detailed profiles were obtained at twelve axial locations (extending from the nozzle exit for a distance of 5 diameters) downstream from a single element of the Bell Aerospace H2/O2 19-element coaxial injector. Measurements of mass-flux per unit area (using a constant temperature anemometer), total pressure and local temperature were used in the determination of local static pressure and velocity. These data show a low pressure region exists near the nozzle exit. Although this pressure reduction is small (0.34 psi), it substantially altered the flow development. Comparison of results shows that velocity near the nozzle exit decreases initially (no central velocity core) as a result of both pressure gradients and viscous mixing. These data are compared with analytical predictions made using available computer codes. Results show the need to consider pressure effects in any proposed mathematical model.

Moon, L. F.↗
NASA NTRS1983

Effects of drift on the transport of cosmic rays. VI - A three-dimensional model including diffusion

The first results are presented from a series of computer simulations of the solar modulation of galactic cosmic rays using a full three-dimensional model which incorporates all known important effects on particle transport, particle drifts, convection with the solar wind, energy loss, and anisotropic diffusion. The model is time-independent in the coordinate frame rotating with the sun, so corotating effects can be studied. Modulation in an interplanetary magnetic field model is considered in which the current sheet separating the northern and southern solar hemispheres is warped and corotating with the sun. The amplitude of the warp is varied to simulate possible solar cycle variation of the magnetic field. Substantial effects due to the warp of the current sheet are found. Comparison of the model results with various data is presented. Among other things, it is shown that the intensity may decrease away from the current sheet for both signs of the magnetic field, as suggested by recent observations, and in contrast with inferences from earlier, more approximate calculations.

Kota, J.↗
NASA NTRS1989

An experimental investigation of a low Reynolds number turbulent boundary layer subject to an adverse pressure gradient

A very low Reynolds number turbulent boundary layer subject to an adverse pressure gradient is studied. The aim is to obtain highly accurate mean-flow and turbulence measurements under conditions that can be closely related to the numerical simulations of Philippe Spalart for the purposes of CFD validation. Much of the Boundary Layer Wind Tunnel was completely rebuilt with a new wider contraction and working section which will improve compatibility with the simulations. A unique sophisticated high-speed computer controlled 3-D probe traversing mechanism was integrated into the test section. Construction of the tunnel and traverse is discussed in some detail. The hardware is now complete, and measurements are in progress. The mean-flow data indicate that a suitably two-dimensional base flow was established. Automation of the probe positioning and data acquistion have led to a decreased running time for total pressure measurements. However, the most significant benefits are expected to occur when using hot-wire probes. Calibrations can be performed automatically and there is no need to handle fragile probes when moving between measuring stations. Techniques are being developed which require sampling of the signals from moving hot-wire probes on the basis of their position in the flow. Measurements can be made in high intensity turbulence by flying probes upstream at high speed so that the relative magnitude of the turbulent velocity fluctuations are reduced. In regions, where the turbulence intensity is not too large, the probe can also be repetitively scanned across very dense spatial grids in other directions. With this technique, a complete profile can be measured in about 1/3 the time and with a spatial density about 50 times that obtainable using a stationary probe.

Watmuff, Jonathan H.↗
NASA NTRS2004

College Bound with the Office of Educational Programs

The Educational Programs Office at NASA Glenn Research Center hosts a variety of programs that takes on the hard task of getting students of all ages interested in pursuing careers in science, mathematics, and engineering. To help assist students along the way there are many programs to participate in such as: the explorers, shadowing opportunities, and paid internships. The Educational Programs Office not only creates learning opportunities for students, they also host workshops to help educators enhance their knowledge these fields. This summer I assisted Marie Borowski in the Educational Programs Office with the Tennessee State University College Bound Program. The Tennessee state University College Bound Program is an intensive two-week summer academic workshop designed to introduce minority students to the profession of engineering. NASA Glenn Research Center sent forty dedicated students on a bus to Nashville, Tennessee to experience college life as a whole. At the college the students day consisted of a math class, aeronautics, ACT/SAT preparation, writing and research, African American Culture, computer science, and study sessions. The students also went on educational field trips to the Fisk Museum, the Space and Rocket Center, and the Parthenon Museum. On the last day of the program the students competed in an oratorical contest where the students made a Powerpoint presentation on the class that they enjoyed the most. There were many processes that had to be put into action for the college bound program to run smoothly. The process started in early January with the preparation of applications. Once prepared, the applications were then sent to schools and past participants in hopes of receiving a well-qualified pool of applicants. Once the applications were received, a prescreening is done which ensures all of the information is complete. Then, they are reviewed by a panel, using a rubric to evaluate them, and the semifinalists are then selected. Interviews are held with the students and their parents had to be interviewed by a panel of judges and graded on a rubric. The scores were added up and the forty students were selected. My job this summer was getting the students ready to leave for Tennessee. My job consisted of working very closely with my mentor, Marie Borowski, compile the student data to provide it to the chaperones, TSU records, and NASA records. I learned about the vital communication between the NASA and the TSU program managers. After all the planning was done and the program had begun I had a chance to fly to Tennessee for six days to observe the students daily activities. The students had adjusted very well to the intense schedule, and seemed very enthusiastic about the activities to follow. The whole group was very attentive and enthusiastic program be longer. My goals for the summer were all met. I wanted to learn and retain all the information I possibly could on the job I was given. I was very happy with the end result.

Neal, Brittany D.↗
DOE OSTI2016

SU-F-T-256: 4D IMRT Planning Using An Early Prototype GPU-Enabled Eclipse Workstation

Purpose: True 4D IMRT planning, based on simultaneous spatiotemporal optimization has been shown to significantly improve plan quality in lung radiotherapy. However, the high computational complexity associated with such planning represents a significant barrier to widespread clinical deployment. We introduce an early prototype GPU-enabled Eclipse workstation for inverse planning. To our knowledge, this is the first GPUintegrated Eclipse system demonstrating the potential for clinical translation of GPU computing on a major commercially-available TPS. Methods: The prototype system comprised of four NVIDIA Tesla K80 GPUs, with a maximum processing capability of 8.5 Tflops per K80 card. The system architecture consisted of three key modules: (i) a GPU-based inverse planning module using a highly-parallelizable, swarm intelligence-based global optimization algorithm, (ii) a GPU-based open-source b-spline deformable image registration module, Elastix, and (iii) a CUDA-based data management module. For evaluation, aperture fluence weights in an IMRT plan were optimized over 9 beams,166 apertures and 10 respiratory phases (14940 variables) for a lung cancer case (GTV = 95 cc, right lower lobe, 15 mm cranio-caudal motion). Sensitivity of the planning time and memory expense to parameter variations was quantified. Results: GPU-based inverse planning was significantly accelerated compared to its CPU counterpart (36 vs 488 min, for 10 phases, 10 search agents and 10 iterations). The optimized IMRT plan significantly improved OAR sparing compared to the original internal target volume (ITV)-based clinical plan, while maintaining prescribed tumor coverage. The dose-sparing improvements were: Esophagus Dmax 50%, Heart Dmax 42% and Spinal cord Dmax 25%. Conclusion: Our early prototype system demonstrates that through massive parallelization, computationally intense tasks such as 4D treatment planning can be accomplished in clinically feasible timeframes. With further optimization, such systems are expected to enable the eventual clinical translation of higher-dimensional and complex treatment planning strategies to significantly improve plan quality. This work was partially supported through research funding from National Institutes of Health (R01CA169102) and Varian Medical Systems, Palo Alto, CA, USA.

60 APPLIED LIFE SCIENCES↗
NASA NTRS1974

Application of ERTS-1 data to the protection and management of New Jersey's coastal environment

The author has identified the following significant results. Rapid access to ERTS data was provided by NASA GSFC for the February 26, 1974 overpass of the New Jersey test site. Forty-seven hours following the overpass computer-compatible tapes were ready for processing at EarthSat. The finished product was ready just 60 hours following the overpass and delivered to the New Jersey Department of Environmental Protection. This operational demonstration has been successful in convincing NJDEP as to the worth of ERTS as an operational monitoring and enforcement tool of significant value to the State. An erosion/ accretion severity index has been developed for the New Jersey shore case study area. Computerized analysis techniques have been used for monitoring offshore waste disposal dumping locations, drift vectors, and dispersion rates in the New York Bight area. A computer shade print of the area was used to identify intensity levels of acid waste. A Litton intensity slice print was made to provide graphic presentation of dispersion characteristics and the dump extent. Continued monitoring will lead to the recommendation and justification of permanent dumping sites which pose no threat to water quality in nearshore environments.

Yunghans, R. S.↗
DOE OSTI2026

Powering Circularity Through Data Reporting and Collection

Sustainability and Circular Economy have many metrics for evaluation. Calculating mass intensity, energy return on investment, financial payback, and recycling rate for proposed technology changes and lifecycle management can support decision making. Robust data with modeling tools can perform these calculations, informing good decision making. Analyses show that reliability is more critical than recyclability. Improved data gathering and tool accessibility will support our industry to make more circular choices for PV lifecycle management.

14 SOLAR ENERGY↗
DOE OSTI2013

Integrating Online Compression to Accelerate Large-Scale Data Analytics Applications

Abstract—With growing dataset sizes, and as computing cycles are increasing faster than storage and wide-area bandwidths, compression appears like a promising approach for improving the performance of large-scale data analytics applications. In this context, this paper makes the following contributions. First, we develop a new compression methodology, which exploits the similarities between spatial and/or temporal neighbors in a simulation dataset, and enables high compression ratios and low decompression costs. Second, we have developed a framework that can be used to incorporate a variety of compression and decompression algorithms. This framework also supports a simple API to allow integration with an existing application or data processing middleware. Once a compression algorithm is implemented, this framework can allow multi-threaded retrieval, multi-threaded data decompression, and use of informed prefetching and caching. By integrating this framework with a data-intensive middleware, we have applied our compression methodology and framework to three applications over two datasets, including a GCRM climate model dataset. We obtained an average compression ratio of 51.68%, and up to 53.27% improvement in execution time of data analysis applications.

Big Data, I/O, HPC↗
DOE OSTI2013

Digital tomosynthesis (DTS) for verification of target position in early stage lung cancer patients

Purpose: The ability to verify intrafraction tumor position is clinically useful for hypofractionated treatments. Short arc kV digital tomosynthesis (DTS) could facilitate more frequent target verification. The authors used DTS combined with triangulation to determine the mean temporal position of small-volume lung tumor targets treated with stereotactic radiotherapy. DTS registration results were benchmarked against online clinical localization using registration between free-breathing cone-beam computed tomography (CBCT) and the average intensity projection (AvIP) of the planning 4DCT.Methods: In this retrospective study, 76 sets of kV-projection images from online CBCT scans of 13 patients were used to generate DTS image slices (CB-DTS) with nonclinical research software (DTS Toolkit, Varian Medical Systems). Three-dimensional tumor motion was 1.3–4 mm in six patients and 6.1–25.4 mm in seven patients on 4DCT (significant difference in the mean of the groups, P < 0.01). The 4DCT AvIP was used to digitally reconstruct the Reference-DTS. DTS registration and DTS registration combined with triangulation were investigated. Progressive shortening of total DTS arc lengths from 95° to 35° around 0° gantry position was evaluated for different scenarios: DTS registration using the entire arc; DTS registration plus triangulation using two nonoverlapping arcs; and for 55° and 45° total gantry rotation, DTS registration plus triangulation using two overlapping arcs. Finally, DTS registration plus triangulation performed at eight gantry angles, each separated by 45° was evaluated using full fan kV projection data for one patient with an immobile tumor and five patients with mobile tumors.Results: For DTS registration alone, shortening arc length did not influence accuracy in X- and Y-directions, but in Z-direction, mean deviations from online CBCT localization systematically increased for shorter arc length (P < 0.05). For example, using a 95° arc mean DTS-CBCT difference was 0.8 mm (1 SD = 0.6 mm) and for a 35° arc the mean was 2.4 mm (1 SD = 1.7 mm). DTS plus triangulation using nonoverlapping-arcs increased accuracy in Z-direction for tested arc lengths ≤55° (P < 0.01). Overlapping arcs increased accuracy in Y-direction for tumors with motion >4 mm (P < 0.02) but increased Z-direction accuracy was only observed with 55° total gantry rotation. The 95th percentile deviations with this overlapping technique in X-, Y-, and Z-directions were 1.3, 2.0, and 2.5 mm, respectively. For the five patients with mobile tumors where DTS + triangulation was performed with 45° intervals, the pooled deviation from online CBCT correction showed, for X-, Y-, and Z-directions, mean of 1.1 mm, standard deviations (SD) of 0.9, 1.0, and 0.9 mm, respectively. The mean + 2 SD was <3 mm for each direction.Conclusions: Short-arc DTS verification of time averaged lung tumor position is feasible using free-breathing kV projection data and the AvIP of the 4DCT as a reference. Observed differences between DTS and online CBCT registration with AvIP were ≤3 mm (mean + 2 SD), however, the increased temporal resolution of DTS + triangulation also identified short period deviations from the average target position on the CBCT. Short-arc DTS appears promising for intrafraction tumor position monitoring during stereotactic lung radiotherapy delivered with a rotational technique.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
NASA NTRS2000

North Atlantic Aerosol Radiative Impacts Based on Satellite Measurements and Aerosol Intensive Properties from TARFOX and ACE-2

We estimate the impact of North Atlantic aerosols on the net short-wave flux at the tropopause by combining satellite-derived aerosol optical depth (AOD) maps with model aerosol properties determined via closure analyses in TARFOX and ACE 2. We exclude African dust, primarily by restricting latitudes to 25-60 N. The analyses use in situ aerosol composition measurements and air- and ship-borne sun-photometer measurements of AOD spectra. The aerosol model yields computed flux sensitivities (dFlux/dAOD) that agree with measurements by airborne flux radiometers in TARFOX. Its midvisible single-scattering albedo is 0.9. which is in the range obtained from in situ measurements of scattering and absorption in both TARFOX and ACE 2. Combining satellite-derived AOD maps with the aerosol model yields maps of 24-hour average net radiative flux changes. For simultaneous AVHRR, radiance measurements exceeded the sunphotometer AODs by about 0.04. However. shipboard sunphotometer and AVHRR AODs agreed Within 0.02 for data acquired during satellite overflights on two other days. We discuss attempts to demonstrate column closure within the MBL by comparing shipboard sunphotometer AODs and values calculated from simultaneous shipboard in-situ aerosol size distribution measurements. These comparisons were mostly unsuccessful, but they illustrate the difficulties inherent in this type of closure analysis. Specifically, AODs derived from near-surface in-situ size distribution measurements are extremely sensitive to the assumed hygroscopic growth model that itself requires an assumption of particle composition as a function of height and size, to the radiosonde-measured relative humidity, and to the vertical profile of particle number. We investigate further the effects of hygroscopic particle growth within the MBL by using shipboard lidar aerosol backscatter profiles together with the sunphotometer AOD.

Russell, P. B.↗
DOE OSTI2024

Peregrine Software Development: Report on the Code Conversion From Python to C++

This work package seeks to convert the Peregrine software tool from its original Python implementation to a production version based on the C++ language. Peregrine is a powerful research platform with a multitude of advanced data analytics and data visualization functionalities. Developed by scientists to explore multimodal and multidimensional data related to the production of components using powder bed additive manufacturing processes, the tool implements state-of-the-art algorithms to assist machine users in making build or part quality determinations. Given that Peregrine is data-intensive, the goal of this conversion is to enhance the tool’s flexibility and interactivity and reduce the number of code dependencies to facilitate its deployment as part of the ongoing technology transfer campaign. This brief document provides an overview of Peregrine’s functionalities and capabilities, along with a detailed description of the core functionalities that have been implemented to date in the new C++ version. This document serves as a development update at the end of the first year of the ongoing conversion and will be regularly updated as progress continues.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

District heating utilizing waste heat of a data center: High-temperature heat pumps

Data centers are energy-intensive facilities with substantial low-grade waste heat. High-temperature heat pumps can be critical in boosting the data center’s waste heat for district heating, improving the system-level energy efficiency of data centers, and reducing CO 2 emissions in district heating. This study built thermodynamic models to assess high-temperature heat pumps with six configurations using low global warming potential refrigerants to supply heat up to 120 °C. The heat pump configurations include single-stage or two-stage cycles with advanced components, such as internal heat exchanger, economizer, flash tank, or parallel compressor. The refrigerants include R1234ze(Z), R1233ed(E), R1224yd(Z), R600, and R600a, and R245fa is used as a reference. A case study was carried out to recover the waste heat from the Frontier high-performance computing data center and provide hot water for district heating at the US Department of Energy’s Oak Ridge National Laboratory campus. The optimized performance of high-temperature heat pumps is characterized with various effectiveness of internal heat exchangers, and the operating parameters of economizer or flash tank, as well as their combination. The results show that the configurations of two-stage cycles with internal heat exchanger + flash tank and internal heat exchanger + economizer/parallel-compressor provide the highest coefficient of performance under scenarios of the maximum allowable value and a fixed value (0.3) of the internal heat exchangers’ effectiveness, respectively. R1234ze(Z) and R600a are the most promising refrigerants, considering trade-offs between the coefficient of performance and the volumetric heating capacity. The single-stage cycle with internal heat exchanger + economizer/parallel-compressor using R1234ze(Z) is recommended for utilizing Fronter’s waste heat in district heating. A one mega-watt high-temperature heat pump will reduce 33,100–33,200 metric tons of CO2 emission annually, corresponding to 85.4 %–85.6 % of equivalent CO2 emissions from natural gas boilers. Here, this study provides good guidelines for designing and deploying high-temperature heat pumps to support sustainable data centers and decarbonize district heating in the US.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2024

Water–Hydrocarbon Interactions in Anionic Pyrene Monohydrate

Interactions between water and polycyclic aromatic hydrocarbons are essential in many aspects of chemistry, from interstellar and atmospheric processes to interfacial hydrophobicity and wetting phenomena. Despite their growing importance, the intermolecular potentials of the water-hydrocarbon interactions are underdeveloped compared to water-water potentials, and there are similarly few experimental probes that are sensitive to the details of the water-hydrocarbon potential. We present a combined experimental and computational study of anionic pyrene monohydrate, one of the simplest water/hydrocarbon clusters. The action spectrum in the OH region of the mass-selected cluster ion provides a rigorous benchmark for intermolecular potentials and computational methodologies. We identify missing intermolecular interactions and shortcomings in conventional dynamics calculations by comparing experimental data to density functional theory and classical molecular dynamics calculations. Kinetic trapping is prevalent, even for one water molecule and one pyrene molecule, leading to slow equilibration in conventional molecular dynamics calculations, even on nanosecond timescales and at low temperatures (50 K). At constant energy, temperature fluctuations for the pair of molecules are substantial. Immersing the system in a bath of soft spheres and employing parallel tempering alleviates kinetic trapping and dampens temperature fluctuations, bringing the system closer to the thermodynamic limit. With such augmented sampling, a simple, flexible water model reproduces the linewidth and the asymmetric broadening of the symmetric OH stretching mode, which we assign to spectral diffusion. In the OH stretching region, dynamics calculations predict a more intense antisymmetric peak than experiments observe but do not predict the bimodal split symmetric peak that the experiments show. Furthermore, our work suggests that electronic polarization, missing in the empirical force field, is responsible for the first discrepancy and that quantum nuclear effects, captured neither in density functional theory nor in classical dynamics, may be responsible for the second.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗