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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

encore : an O ( N g2) estimator for galaxy N -point correlation functions

ABSTRACT We present a new algorithm for efficiently computing the N-point correlation functions (NPCFs) of a 3D density field for arbitrary N. This can be applied both to a discrete spectroscopic galaxy survey and a continuous field. By expanding the statistics in a separable basis of isotropic functions built from spherical harmonics, the NPCFs can be estimated by counting pairs of particles in space, leading to an algorithm with complexity $\mathcal {O}(N_\mathrm{g}^2)$ for Ng particles, or $\mathcal {O}(N_\mathrm{FFT}\log N_\mathrm{FFT})$ when using a Fast Fourier Transform with NFFT grid-points. In practice, the rate-limiting step for N > 3 will often be the summation of the histogrammed spherical harmonic coefficients, particularly if the number of radial and angular bins is large. In this case, the algorithm scales linearly with Ng. The approach is implemented in the encore code, which can compute the 3PCF, 4PCF, 5PCF, and 6PCF of a BOSS-like galaxy survey in ${\sim}100$ CPU-hours, including the corrections necessary for non-uniform survey geometries. We discuss the implementation in depth, along with its GPU acceleration, and provide practical demonstration on realistic galaxy catalogues. Our approach can be straightforwardly applied to current and future data sets to unlock the potential of constraining cosmology from the higher point functions.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Photon–photon chemical thermodynamics of frequency conversion processes in highly multimode systems

Abstract Frequency generation in highly multimode nonlinear optical systems is inherently a complex process, giving rise to an exceedingly convoluted landscape of evolution dynamics. While predicting and controlling the global conversion efficiencies in such nonlinear environments has long been considered impossible, here, we formally address this challenge even in scenarios involving a very large number of spatial modes. By utilizing fundamental notions from optical statistical mechanics, we develop a universal theoretical framework that effectively treats all frequency components as chemical reactants/products, capable of undergoing optical thermodynamic reactions facilitated by a variety of multi-wave mixing effects. These photon–photon reactions are governed by conservation laws that directly determine the optical temperatures and chemical potentials of the ensued chemical equilibria for each frequency species. In this context, we develop a comprehensive stoichiometric model and formally derive an expression that relates the chemical potentials to the optical stoichiometric coefficients, in a manner akin to atomic/molecular chemical reactions. This advancement unlocks new predictive capabilities that can facilitate the optimization of frequency generation in highly multimode photonic arrangements, surpassing the limitations of conventional schemes that rely exclusively on nonlinear optical dynamics. Notably, we identify a universal regime of Rayleigh–Jeans thermalization where an optical reaction at near-zero optical temperatures can promote the complete and entropically irreversible conversion of light to the fundamental mode at a target frequency. Our theoretical results are corroborated by numerical simulations in settings where second-harmonic generation, sum-frequency generation and four-wave mixing processes can manifest.

Optics↗
DOE OSTI2020

NRC Multiphysics Analysis Capability Deployment FY2020 - Part 4

This report details progress and activities of Idaho National Laboratory (INL) on the Nuclear Regulatory Commission (NRC) project “Development and Modeling Sup- port for Advanced Non-Light Water Reactors.” The tasks completed for this report are: • Task 3a: This task demonstrates the effectiveness of Griffin’s methods for interpolating cross sections and SPH correction factors as a function of control drum rotation. The Monte Carlo code Serpent is used to generate reference results. The accuracy of Griffin-calculated eigenvalues and reaction rates are studied as a function of control drum rotation for cross section and SPH factor libraries of varying fidelity. Higher-fidelity libraries require less interpolation and are therefore inherently more accurate; however, they require more computational resources to create. Overall, Griffin is able to accurately model eigenvalue and reaction rates over the full range of drum rotation using a library generated from three to five discrete drum rotations for a particular microreactor design. • Task 3c: This preliminary task successfully demonstrates the performance of a coupled neutron-photon transport calculation with Griffin using the spherical harmonics approximation. The Griffin solutions are compared to reference solutions from the continuous energy Monte Carlo codes MCNP and Serpent. Furthermore, this work also demonstrates how to prepare the neutron and photon libraries using NJOY, MCNP, and Serpent with the latest ENDF/B-VIII data for 235 U and graphite. The Griffin total energy deposition in the active core region is calculated within 0.3% of the reference, but it degrades in the reflector regions with a maximum difference of -1.5%. Overall, the results look promising and future analysis should use an improved data stream and focus on determining the potential cancellation of error within each energy group.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2022

Adapting Technology Learning Curves for Prospective Techno-Economic and Life Cycle Assessments of Emerging Carbon Capture and Utilization Pathways

Comparisons of emerging carbon capture and utilization (CCU) technologies with equivalent incumbent technologies are necessary to support technology developers and to help policy-makers design appropriate long-term incentives to mitigate climate change through the deployment of CCU. In particular, early-stage CCU technologies must prove their economic viability and environmental reduction potential compared to already-deployed technologies. These comparisons can be misleading, as emerging technologies typically experience a drastic increase in performance and decrease in cost and greenhouse gas emissions as they develop from research to mass-market deployment due to various forms of learning. These changes complicate the interpretation of early techno-economic assessments (TEAs) and life cycle assessments (LCAs) of emerging CCU technologies. The effects of learning over time or cumulative production themselves can be quantitatively described using technology learning curves (TLCs). While learning curve approaches have been developed for various technologies, a harmonized methodology for using TLCs in TEA and LCA for CCU in particular is required. To address this, we describe a methodology that incorporates TLCs into TEA and LCA to forecast the environmental and economic performance of emerging CCU technologies. This methodology is based on both an evaluation of the state of the art of learning curve assessment and a literature review of TLC approaches developed in various manufacturing and energy generation sectors. Additionally, we demonstrate how to implement this methodology using a case study on a CO 2 mineralization pathway. Finally, commentary is provided on how researchers, technology developers, and LCA and TEA practitioners can advance the use of TLCs to allow for consistent, high-resolution modeling of technological learning for CCU going forward and enable holistic assessments and fairer comparisons with other climate technologies.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2024

Efficient laser-driven proton acceleration from a petawatt contrast-enhanced second harmonic mixed-glass laser system

Efficient laser-driven plasma acceleration of ion beams requires precision control of the target–plasma profile, which is crucial to optimize the laser energy transfer. Along the laser propagation direction, this can be achieved by tailoring the temporal structure of the laser pulse. We show for the first time that frequency-doubling of a short pulse (hundreds-femtosecond range) petawatt-class mixed-glass laser system, which results in temporal intensity contrast enhancement, enables surface and volumetric laser–energy coupling, and the acceleration of proton beams from few-nanometer-thick foil targets. Experimentally, maximum ion energies and laser-to-proton energy conversion efficiencies were found to be both maximized at optimum laser and target conditions manifested when the normalized target density nearly equalizes the normalized laser vector potential, which is in agreement with theory and simulations. These signatures are recognized as a unique indication of the interaction between ultra-intense laser pulses with high temporal intensity contrast and ultra-thin nanometer-scale targets. Transverse modulations of accelerated proton beams in the form of bubble- and ring-like structures measured in the thinnest targets provide additional evidence of volumetric laser-driven particle acceleration regimes and transitional features in ultra-thin foil targets specific to laser–plasma interactions characterized by a high temporal intensity contrast. These results open avenues in the generation of high contrast laser pulses from short-pulse-femtosecond petawatt mixed-glass laser systems and demonstrate the feasibility of this technique for applications requiring high laser intensity contrast with high efficiency.

Physics↗
DOE OSTI2023

Nonlinear dynamics, bifurcations, and multi-stability in a vibro-impact system with geometric and multi-segmented freeplay nonlinearities

Freeplay is a common type of piecewise-smooth nonlinearity in dynamical systems, and it can cause discontinuity-induced bifurcations and other behaviors that may bring about undesirable and potentially damaging responses. Prior research has focused on piecewise-smooth systems with two or three distinct regions, but less attention is devoted to systems with more regions (i.e., multi-segmented systems). In this work, numerical analysis is performed on a dynamical system with multi-segmented freeplay, in which there are four stiffness transitions and five distinct regions in the phase space. Here, the effects of the multi-segmented parameters are studied through bifurcation diagram evolution along with induced multi-stable behavior and different bifurcations. These phenomena are interrogated through various tools, such as harmonic balance, basins of attraction, phase planes, and Poincaré section analysis. Results show that among the three multi-segmented parameters, the asymmetry has the strongest effect on the response of the system.

42 ENGINEERING↗
DOE OSTI2022

SIT 45: An interacting, compact, and star-forming isolated galaxy triplet

The underlying scenario of the formation and evolution of galaxy triplets is still uncertain. Mergers of galaxies in isolated triplets give us the opportunity to study the already complex merging process, with minimal contamination of other environmental effects that potentially allow and accelerate galaxy transitions from active star-forming to passive galaxies. The merging system SIT 45 (UGC 12589) is one of 315 systems in the SDSS-based catalogue of Isolated Triplets (SIT); it is an unusual isolated galaxy triplet, consisting of three merging late-type galaxies. The main aims of this work are to study the dynamical evolution and star formation history (SFH) of SIT 45, as well as its dependence on its local and large-scale environment. Methods. To study its dynamics, parameters such as the velocity dispersion (σ v ), the harmonic radius (R H ), the crossing time (H 0 t c ), and the virial mass (M vir ), along with the compactness of the triplet (S) were considered. To investigate the possible dependence of these dynamical parameters on the environment, the tidal force Q parameters (both local and large-scale) and the projected local density (η k ) were used. To constrain the SFH, we used CIGALE to fit its observed spectral energy distribution using multiwavelength data from the ultraviolet to the infrared. SIT 45 is one of the most compact triplets in the SIT, and it is also more compact than triplets in other samples. According to its SFH, SIT 45 presents star formation, where the galaxies also present recent (~200 Myr) star formation increase, indicating that this activity may have been triggered by the interaction. Its dynamical configuration suggests that the system is highly evolved in comparison to the SIT. However, this is not expected for systems composed of star-forming late-type galaxies, based on observations in compact groups. We conclude that SIT 45 is a system of three interacting galaxies that are evolving within the same dark matter halo; its compact configuration is a consequence of the ongoing interaction rather than being due to a long-term evolution (as suggested from its H 0 t c value). We consider two scenarios for the present configuration of the triplet, one where one of the members is a tidal galaxy, and another where this galaxy arrives to the system after the interaction. Both scenarios need further exploration. The isolated triplet SIT 45 is therefore an ideal system to study short timescale mechanisms (~10 8 yr), such as starbursts triggered by interactions which are more frequent at higher redshift.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Two-XUV-photon double ionization of neon

Two XUV-photon double ionization of Ne, induced by an intense few-pulse attosecond train with a ~ 4 fs envelope duration is investigated experimentally and theoretically. The experiment is performed at ELI-ALPS utilizing the recently constructed 10 Hz gas phase high-order harmonic generation SYLOS GHHG-COMPACT beamline. A total pulse energy up to ~1 {\mu}J generated in Argon in conjunction with high reflectivity optics in the XUV region, allowed the observation of the doubly charged state of Ne induced by 40 eV central XUV photon energies. The interaction of the intense attosecond pulse train with Ne is also theoretically studied via a second-order time dependent perturbation theory equations-of-motion. Further, the results of this work, combined with the feasibility of conducting XUV-pump-XUV-probe experiments, constitute a powerful tool for many potential applications. Those include attosecond pulse metrology as well as time resolved investigations of the dynamics underlying direct and sequential double ionization and their electron correlation effects.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Quadrature Based Neural Network Learning of Stochastic Hamiltonian Systems

Hamiltonian Neural Networks (HNNs) provide structure-preserving learning of Hamiltonian systems. In this paper, we extend HNNs to structure-preserving inversion of stochastic Hamiltonian systems (SHSs) from observational data. We propose the quadrature-based models according to the integral form of the SHSs’ solutions, where we denoise the loss-by-moment calculations of the solutions. The integral pattern of the models transforms the source of the essential learning error from the discrepancy between the modified Hamiltonian and the true Hamiltonian in the classical HNN models into that between the integrals and their quadrature approximations. This transforms the challenging task of deriving the relation between the modified and the true Hamiltonians from the (stochastic) Hamilton–Jacobi PDEs, into the one that only requires invoking results from the numerical quadrature theory. Meanwhile, denoising via moments calculations gives a simpler data fitting method than, e.g., via probability density fitting, which may imply better generalization ability in certain circumstances. Numerical experiments validate the proposed learning strategy on several concrete Hamiltonian systems. The experimental results show that both the learned Hamiltonian function and the predicted solution of our quadrature-based model are more accurate than that of the corrected symplectic HNN method on a harmonic oscillator, and the three-point Gaussian quadrature-based model produces higher accuracy in long-time prediction than the Kramers–Moyal method and the numerics-informed likelihood method on the stochastic Kubo oscillator as well as other two stochastic systems with non-polynomial Hamiltonian functions. Moreover, the Hamiltonian learning error εH arising from the Gaussian quadrature-based model is lower than that from Simpson’s quadrature-based model. These demonstrate the superiority of our approach in learning accuracy and long-time prediction ability compared to certain existing methods and exhibit its potential to improve learning accuracy via applying precise quadrature formulae.

Mathematics↗
DOE OSTI2024

Constraining gravity with a new precision 𝐸 𝐺 estimator using Planck + SDSS BOSS data

The 𝐸 𝐺 statistic is a discriminating probe of gravity developed to test the prediction of general relativity (GR) for the relation between gravitational potential and clustering on the largest scales in the observable Universe. We present a novel high-precision estimator for the 𝐸 𝐺 statistic using CMB lensing and galaxy clustering correlations that carefully matches the effective redshifts across the different measurement components to minimize corrections. A suite of detailed tests is performed to characterize the estimator’s accuracy, its sensitivity to assumptions and analysis choices, and the non-Gaussianity of the estimator’s uncertainty is characterized. After finalization of the estimator, it is applied to Planck CMB lensing and SDSS CMASS and LOWZ galaxy data. We report the first harmonic space measurement of 𝐸 𝐺 using the LOWZ sample and CMB lensing and also updated constraints using the final CMASS sample and the latest Planck CMB lensing map. We find $\hat{𝐸}$$^{Planck+CMASS}_{𝐺}$ = 0.3⁢6$^{+0.06}_{−0.05}$⁢(68.27%) and $\hat{𝐸}$$^{Planck+LOWZ}_{𝐺}$ = 0.4⁢0$^{+0.11}_{−0.09}$⁢(68.27%), with additional subdominant systematic error budget estimates of 2% and 3%, respectively. Using Ω m,0 constraints from Planck and SDSS BAO observations, Λ⁢CDM-GR predicts 𝐸$^{GR}_ {𝐺}$⁡(𝑧 =0.555) = 0.401 ± 0.005 and 𝐸$^{GR}_{𝐺}$⁡(𝑧 =0.316) = 0.452 ± 0.005 at the effective redshifts of the CMASS and LOWZ based measurements. We report the measurement to be in good statistical agreement with the Λ⁢CDM-GR prediction and report that the measurement is also consistent with the more general GR prediction of scale independence for 𝐸 𝐺 . Furthermore, this work provides a carefully constructed and calibrated statistic with which 𝐸 𝐺 measurements can be confidently and accurately obtained with upcoming survey data.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Inverse design for waveguide dispersion with a differentiable mode solver

Inverse design of optical components based on adjoint sensitivity analysis has the potential to address the most challenging photonic engineering problems. However, existing inverse design tools based on finite-difference-time-domain (FDTD) models are poorly suited for optimizing waveguide modes for adiabatic transformation or perturbative coupling, which lies at the heart of many important photonic devices. Among these, dispersion engineering of optical waveguides is especially challenging in ultrafast and nonlinear optical applications involving broad optical bandwidths and frequency-dependent anisotropic dielectric material response. In this work, we develop gradient back-propagation through a general-purpose electromagnetic eigenmode solver and use it to demonstrate waveguide dispersion optimization for second harmonic generation with maximized phase-matching bandwidth. This optimization of three design parameters converges in eight steps, reducing the computational cost of optimization by ∼100x compared to exhaustive search and identifying new designs for broadband optical frequency doubling of laser sources in the 1.3–1.4 µm wavelength range. Furthermore, we demonstrate that the computational cost of gradient back-propagation is independent of the number of parameters, as required for optimization of complex geometries. This technique enables practical inverse design for a broad range of previously intractable photonic devices.

Gray, Dodd (ORCID:000000030469599X)↗
DOE OSTI2021

Novel Geochemistry Determined from High Pressure, High Temperature Simulation Experiments of Hydraulic Fracture Test Site 2

A standard method in unconventional oil and gas production is the process of hydraulic fracturing followed by a shut-in period, during which the fracture fluid remains pressurized in the reservoir for up to three weeks before production begins. Despite this widely used process, very little is known about what occurs in the reservoir during this shut-in process. In order to properly delineate potential reservoir reactions that may occur during shut-in that would lead to corrosion and scaling events, experiments were conducted in high pressure, high temperature reactors to simulate conditions of the Wolfcamp Formation in the Delaware Basin. Experimental design allowed the assessment of the effect of proppant, microbiology, and time on the mineralogy and fluid chemistry in the reservoir. Results suggest the biggest impact on fluid chemistry and shale mineralogy during shut-in is time. Analyses demonstrate dissolution of the shale material, with maximum dissolved ions occurring after 7 days of the shut-in period. After 21 days, results suggest precipitation occurs. The Delaware Basin is demonstrated to be high in sulfate content, which further increases in the fluid due to dissolution reactions during shut-in. The pressure vessel experiments suggest there was no significant contribution to reactions from microbiology during the shut-in period. Furthermore, early production samples demonstrate a significant selection of the microorganism Caminicella, a genus of which has previously been correlated to corrosion and sulfide production. Results suggest shut-in conditions may provide high sulfate concentrations that could later be utilized by a shifted microbial community to drive potential well infrastructure failure. This is the first study to incorporate microbiology, mineralogy, and fluid chemistry to investigate the fundamental geochemical reactions that occur during shut-in and early phase production of the Delaware Downloaded from http://onepetro.org/URTECONF/proceedings-pdf/21URTC/2-21URTC/D021S032R001/2477425/urtec-2021-5219-ms.pdf/1 by Carol Worster on 28 February 2022 Basin. Results from this study can complement observations from the Hydraulic Fracture Test Site 2 observations

58 GEOSCIENCES↗
DOE OSTI2023

ESR Dipole Power Supply Current Ripple and Noise Specifications

This note presents key findings for the ESR main magnet dipole power supplies (PS), where we find the current ripple specification to be close to or beyond the state-of-the-art. These specifications originate from beam-beam considerations, with the requirement to limit the ripple-induced hadron emittance growth to below 10%/hour. Beam dynamics that drive this PS ripple specification arise from the beam motions at the Interaction Point (IP). The frequency of the motions can be separated into "low", compared to the betatron frequency, and "high", i.e. around the betatron frequency and harmonics. In terms of the driving frequency, "low" implies ƒ<<ƒ 0 v x,y and "fast" means ƒ≈{ƒ 0 v x,y , ƒ 0 (1- v x,y , etc.}, where ƒ 0 =1/ T 0 =78.2 kHz is the revolution frequency, and v x,y are the fractional parts of the betatron tunes. Frequencies higher than ƒ 0 /2 will be folded back due to the particles sampling the field once per turn. To provide flexibility for future lattice adjustments and working point variations, we do not consider the tunes as fixed. Instead, we assume a certain margin and allow them to potentially fall within the range of 0.1< v x,y <0.5. In other words, the high-frequency region spans approximately from 8kHz to 40 kHz. Consequently,, we definte the dipole PS ripple in two distinct frequency ranges: the low-frequency range of [1-8000] Hz and the high-frequency range of [8-40] kHz. For the physics effects we analyzed in this note, there is no distinction between the ripple (which can be approximately reproduced in the frequency domain) and the random noise if both have some power within the frequency bandwidth of interest. Therefore, while we will use the term "ripple" for short, it should always be understood that we are referring to "ripple plus noise." Except for the lower end of the low-frequency range, the impact of the rippling PS current on the beam will be considerably reduced due to the eddy currents induced in the walls of the vacuum chamber. We will account for this effect in the PS ripple specifications to follow. The remaining sections of this note are structure as follows: Section II outlines the beam-beam physics requirements for the positional stability of the beam at the IP. Section III describes the anticipated shielding effect of the eddy currents induced in the vacuum chamber. Section IV derives the ripple requirement for the low-frequency range by propagating the closed orbit ripple resulting from the rippling dipoles to the IP (relevant lattice simulation results are summarized in the Appendix). In Section V, we present the analytical criterion for the ripple in the high-frequency range by considering resonant oscillations of the electron beam around a stable closed orbit near the betatron frequency. Finally, Section VI provides a summary of our findings and discusses related work.

43 PARTICLE ACCELERATORS↗
DOE OSTI2020

Current measurements in the intermittent-contact mode of atomic force microscopy using the Fourier method: a feasibility analysis

Atomic force microscopy (AFM) is an important tool for measuring a variety of nanoscale surface properties, such as topography, viscoelasticity, electrical potential and conductivity. Some of these properties are measured using contact methods (static contact or intermittent contact), while others are measured using noncontact methods. Some properties can be measured using different approaches. Conductivity, in particular, is mapped using the contact-mode method. However, this modality can be destructive to delicate samples, since it involves continuously dragging the cantilever tip on the surface during the raster scan, while a constant tip–sample force is applied. In this paper we discuss a possible approach to develop an intermittent-contact conductive AFM mode based on Fourier analysis, whereby the measured current response consists of higher harmonics of the cantilever oscillation frequency. Such an approach may enable the characterization of soft samples with less damage than contact-mode imaging. To explore its feasibility, we derive the analytical form of the tip–sample current that would be obtained for attractive (noncontact) and repulsive (intermittent-contact) dynamic AFM characterization, and compare it with results obtained from numerical simulations. Although significant instrumentation challenges are anticipated, the modelling results are promising and suggest that Fourier-based higher-harmonics current measurement may enable the development of a reliable intermittent-contact conductive AFM method.

14 SOLAR ENERGY↗
DOE OSTI2021

Neural Network Sampling of the Free Energy Landscape for Nitrogen Dissociation on Ruthenium

In heterogeneous catalysis, free energy profiles of reactions govern the mechanisms, rates, and equilibria. Energetics are conventionally computed using the harmonic approximation (HA), which requires determination of critical states a priori. Here, we use neural networks to efficiently sample and directly calculate the free energy surface (FES) of a prototypical heterogeneous catalysis reaction—the dissociation of molecular nitrogen on ruthenium—at density-functional-theory-level accuracy. We find that the vibrational entropy of surface atoms, often neglected in HA for transition metal catalysts, contributes significantly to the reaction barrier. The minimum free energy path for dissociation reveals an “on-top” adsorbed molecular state prior to the transition state. While a previously reported flat-lying molecular metastable state can be identified in the potential energy surface, it is absent in the FES at relevant reaction temperatures. Finally, these findings demonstrate the importance of identifying critical points self-consistently on the FES for reactions that involve considerable entropic effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Effect of Collective Dynamics and Anharmonicity on Entropy in Heterogenous Catalysis: Building the Case for Advanced Molecular Simulations

In this paper, we present a perspective on the computational determination of entropy and its effects and consequences on heterogeneous catalysis. Special attention is paid to the role of anharmonicity and the deviations from the standard harmonic oscillator approximations which can fail to provide a reliable assessment of entropy. To address these challenges, advanced methodologies are needed that can explicitly account for these thermodynamic drivers through the appropriate statistical sampling of reactive free energy surfaces. We discuss where anharmonicity should be expected, where it has been observed from a theoretical perspective, and the methods currently employed to address it. We concentrate on three types of systems where we have observed major, nonnegligible anharmonic effects: (1) supported nanoparticles, where the migration of metal atoms, complexes, and entire clusters exhibit anharmonic behavior in their dynamic motion; (2) porous solids where confinement effects distort potential energy surfaces and hinder molecular motions resulting in large entropic terms; and (3) solid/liquid interfaces, where interactions between solvent molecules and adsorbed species can result in large solvent organization free energy and unique reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Above-threshold multiphoton photoemission from noble metal surfaces

Exciting solids with intense femtosecond laser pulses prompts electrons of the interrogated material to respond in a highly nonlinear manner, as is evident in the emission of high-order harmonic radiation and photoelectrons with kinetic energies well above that of the driving photons. Such high-field interactions can be resolved, for example, in above-threshold multiphoton photoemission (ATP) spectroscopy. In this work, we interrogate the nonlinear photoelectric responses of the pristine copper, silver, and gold noble metal surfaces in (111) and (100) crystal orientations in the perturbative regime. Using multiphoton photoemission spectroscopy (mPP) excited by finely tuned optical fields, we characterize enhancement of the mPP and ATP yields from (111) surfaces in selected k||-momentum ranges when the occupied Shockley surface (SS) states are (near-)resonantly coupled by multiphoton transitions to image potential (IP) intermediate states in the excitation process. The ATP signal from the IP states of (111) surfaces is largely defined by their formation through polarization of SS electrons; this observation is contrasted with ATP experiments from the Ag(100) surface, for which the SS becomes an unoccupied resonance and the IP states can only be excited from bands with significantly more bulk character. In addition, based on the optical power and nonlinear order-dependent mPP spectra, we provide evidence for ATP being a one-step, rather than a sequential process, as previously postulated.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

A Comparative Techno-Economic Analysis of Sustainable Methanol Synthesis Pathways from Biomass and CO2

The call to reduce global CO2 emissions is at the forefront of research and development in the transportation and petrochemical industries. A potential solution which intersects both sectors is the adoption and commercialization of more sustainable technologies for methanol production. Currently, methanol is gaining popularity as a possible fuel additive, and as a polymer precursor via established methanol-to-olefins routes which are increasing in capacity and utilization, putting methanol in the spotlight and global methanol production on the rise. At the same time, experimental and computational studies have surged, illuminating a wide array of novel process designs to introduce sustainable methanol into the market. However, with numerous competing pathways identified across a variety of fossil and non-fossil feedstocks, there is a need to harmonize the analyses of these pathways using a consistent techno-economic approach and compare them to current commercial pathways to better understand the benefits or limitations inherent to each technology. In this work we conduct a consistent comparative analysis of three sustainable methanol synthesis pathways versus a commercial baseline, with biomass, CO2, and natural gas as the carbon sources. The three sustainable pathways of interest are biomass gasification to syngas with subsequent catalytic conversion of syngas to methanol, indirect conversion of CO2 to syngas via electrolysis with subsequent catalytic conversion of syngas to methanol, and direct conversion of CO2 to methanol via electrolysis. To elucidate the challenges and opportunities in the path to commercialization of each sustainable pathway, we investigate five key process metrics: production cost, carbon efficiency, carbon intensity, energy efficiency, and technology readiness level (TRL).

biomass↗