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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Impact of penetrating collisions of plasma ions on spectral line shapes

Spectral-line-broadening models have been moving towards including full Coulomb interactions between the atom and plasma, replacing the commonly used dipole approximation. The effects of the full Coulomb interaction have been thoroughly explored for plasma electrons, resulting in redshifts of spectral lines in high-energy-density plasmas. We explore the impact of a full Coulomb treatment on ion broadening. Penetrating collisions due to ions do not significantly impact the linewidths. The most significant aspect is the appearance of quasimolecular resonances in the far line wings, such as those previously observed in white-dwarf spectra. We identify several problems with the existing models. The most direct implementation causes the quasimolecular features to appear at the wrong photon energies. It is possible to include the detailed molecular structure, but this currently requires the Anderson-Talman approximation, which ignores the N-body properties of the plasma. We find that N-body effects can substantially broaden these quasimolecular features and even shift them, depending on the plasma conditions. We conclude that penetration of ions into the spatial extent of the radiator wave function does not strongly affect the usual diagnostics and may have a moderate to weak effect on opacity. Furthermore, the Rosseland mean opacity is weighted towards low-opacity regions of a spectrum, where these quasimolecular features are found.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Introduction to spectral line shape theory

Spectral line-shape models are an important part of understanding high-energy-density (HED) plasmas. Models are needed for calculating opacity of materials and can serve as diagnostics for astrophysical and laboratory plasmas. However, much of the literature on line shapes is directed toward specialists. This perspective makes it difficult for non-specialists to enter the field. We have two broad goals with this topical review. First, we aim to give information so that others in HED physics may better understand the current field. Additionally, this first goal may help guide future experiments to test different aspects of the theory. Second, we provide an introduction for those who might be interested in line-shape theory, and enough materials to be able to navigate the field and the literature. We give a high-level overview of line broadening process, as well as dive into the formalism, available methods, and approximations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Theory of Photoluminescence Spectral Line Shapes of Semiconductor Nanocrystals

Single-molecule photoluminescence (PL) spectroscopy of semiconductor nanocrystals (NCs) reveals the nature of exciton–phonon interactions in NCs. Understanding the homogeneous spectral line shapes and their temperature dependence remains an open problem. Here, we develop an atomistic model to describe the PL spectrum of NCs, accounting for excitonic effects, phonon dispersion relations, and exciton–phonon couplings. We validate our model using single-NC measurements on CdSe/CdS NCs from T = 4 to 290 K, and we find that the slightly asymmetric main peak at low temperatures is comprised of a narrow zero-phonon line (ZPL) and acoustic phonon sidebands. Furthermore, we identify the specific phonon modes that give rise to the optical phonon sidebands. At temperatures above 200 K, the spectral line width shows a stronger dependence upon the temperature, which we demonstrate to be correlated with higher order exciton–phonon couplings. We also identify the line width dependence upon reorganization energy, NC core sizes, and shell thicknesses.

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

Tunnel-FET Switching Is Governed by Non-Lorentzian Spectral Line Shape

In tunnel field-effect transistors (tFETs), the preferred mechanism for switching occurs by alignment (on) or misalignment (off) of two energy levels or band edges. Unfortunately, energy levels are never perfectly sharp. When a quantum dot interacts with a wire, its energy is broadened. Its actual spectral shape controls the current/voltage response of such transistor switches, from on (aligned) to off (misaligned). The most common model of spectral line shape is the Lorentzian, which falls off as reciprocal energy offset squared. Unfortunately, this is too slow a turnoff, algebraically, to be useful as a transistor switch. Electronic switches generally demand an on/off ratio of at least a million. Steep exponentially falling spectral tails would be needed for rapid off-state switching. This requires a new electronic feature, not previously recognized: narrowband, heavy-effective mass, quantum wire electrical contacts, to the tunneling quantum states. These are a necessity for spectrally sharp switching.

42 ENGINEERING↗
DOE OSTI2021

Solid-Density Ion Temperature from Redshifted and Double-Peaked Stark Line Shapes

Heβ spectral line shapes are important for diagnosing temperature and density in many dense plasmas. This work presents Heβ line shapes measured with high spectral resolution from solid-density plasmas with minimized gradients. The line shapes show hallmark features of Stark broadening, including quantifiable redshifts and double-peaked structure with a significant dip between the peaks; these features are compared to models through a Markov chain Monte Carlo framework. Line shape theory using the dipole approximation can fit the width and peak separation of measured line shapes, but it cannot resolve an ambiguity between electron density n e and ion temperature T i , since both parameters influence the strength of quasistatic ion microfields. Here a line shape model employing a full Coulomb interaction for the electron broadening computes self-consistent line widths and redshifts through the monopole term; redshifts have different dependence on plasma parameters and thus resolve the n e – T i ambiguity. The measured line shapes indicate densities that are 80–100% of solid, identifying a regime of highly ionized but well-tamped plasma. This analysis also provides the first strong evidence that dense ions and electrons are not in thermal equilibrium, despite equilibration times much shorter than the duration of x-ray emission; cooler ions may arise from nonclassical thermalization rates or anomalous energy transport. Furthermore, the experimental platform and diagnostic technique constitute a promising new approach for studying ion-electron equilibration in dense plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

The effects of advanced spectral line shapes on atmospheric carbon dioxide retrievals

Line shape effects such as speed-dependence and collisional (Dicke) narrowing are manifest in high signal-to-noise ratio laboratory spectra for a wide range of molecular species and sample conditions. However, these effects are usually neglected in spectroscopic models used in remote sensing of atmospheric greenhouse gases. Here, in this study, we examine the effects of line profile choice on laboratory spectra and XCO 2 values retrieved from Total Carbon Column Observing Network (TCCON) spectra. To this end, we utilize limiting cases of the Hartmann-Tran profile (HTP) with shape parameters recently measured by cavity ring-down spectroscopy. Significant differences highlighting the importance of including speed-dependence effects in forward models were observed both in scaling retrievals as well as profile retrievals. However, because of uncertainties associated with the atmospheric temperature gradient, it was not possible to extract accurate carbon column profiles even with inclusion of these new line shape parameters and advanced line profiles.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Stochastic exciton-scattering theory of optical line shapes: Renormalized many-body contributions

Spectral line shapes provide a window into the local environment coupled to a quantum transition in the condensed phase. In this paper, we build upon a stochastic model to account for non-stationary background processes produced by broad-band pulsed laser stimulation, as distinguished from those for stationary phonon bath. In particular, we consider the contribution of pair-fluctuations arising from the full bosonic many-body Hamiltonian within a mean-field approximation, treating the coupling to the system as a stochastic noise term. Herein, using the Itô transformation, we consider two limiting cases for our model, which lead to a connection between the observed spectral fluctuations and the spectral density of the environment. In the first case, we consider a Brownian environment and show that this produces spectral dynamics that relax to form dressed excitonic states and recover an Anderson–Kubo-like form for the spectral correlations. In the second case, we assume that the spectrum is Anderson–Kubo like and invert to determine the corresponding background. Using the Jensen inequality, we obtain an upper limit for the spectral density for the background. The results presented here provide the technical tools for applying the stochastic model to a broad range of problems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

All-Order Full-Coulomb Quantum Spectral Line-Shape Calculations

Understanding how atoms interact with hot dense matter is essential for astrophysical and laboratory plasmas. Interactions in high-density plasmas broaden spectral lines, providing a rare window into interactions that govern, for example, radiation transport in stars. However, up to now, spectral line-shape theories employed at least one of three common approximations: second-order Taylor treatment of broadening operator, dipole-only interactions between atom and plasma, and classical treatment of perturbing electrons. In this Letter, we remove all three approximations simultaneously for the first time and test the importance for two applications: neutral hydrogen and highly ionized magnesium and oxygen. Finally, we found 15%–50% change in the spectral line widths, which are sufficient to impact applications including white-dwarf mass determination, stellar-opacity research, and laboratory plasma diagnostics.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Controlling laser-dressed resonance line shape using attosecond extreme-ultraviolet pulse with a spectral minimum

High-harmonic generation from a gas target exhibits sharp spectral features and rapid phase variation near the Cooper minimum. By applying spectral filtering, shaped isolated attosecond pulses can be generated where the pulse is split into two in the time domain. Using such shaped extreme-ultraviolet (XUV) pulses, we theoretically study attosecond transient absorption (ATA) spectra of helium 2s2p autoionizing state which is resonantly coupled to the 2s 2 dark state by a time-delayed infrared laser. Our simulations show that the asymmetric 2s2p Fano line shape can be readily tuned into symmetric Lorentzian within the time delay of a few tens of attoseconds. Such efficient control is due to the destructive interference in the generation of the 2s2p state when it is excited by a strongly shaped XUV pulse. This is to be compared to prior experiments where tuning the line shape of a Fano resonance would take tens of femtoseconds. We also show that the predicted ATA spectral line shape can be observed experimentally after propagation in a gas medium. Our results suggest that strongly shaped attosecond XUV pulses offer the opportunity for controlling and probing fine features of narrow resonances on the few-ten attoseconds timescale.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Axial H-Bonding Solvent Controls Inhomogeneous Spectral Broadening, While Peripheral H-Bonding Solvent Controls Vibronic Broadening: Cresyl Violet in Methanol

The dynamics of the nuclei of both a chromophore and its condensed-phase environment control many spectral features, including the vibronic and inhomogeneous broadening present in spectral line shapes. For the cresyl violet chromophore in methanol, we here analyze and isolate the effect of specific chromophore–solvent interactions on simulated spectral densities, reorganization energies, and linear absorption spectra. Employing both chromophore and its condensed-phase environment control many spectral features, including the vibronic and inhomogeneous broadening present in spectral line shapes. For the cresyl violet chromophore in methanol, we here analyze and isolate the effect of specific chromophore–solvent interactions on simulated spectral densities, reorganization energies, and linear absorption spectra. Employing both force field and ab initio molecular dynamics trajectories along with the inclusion of only certain solvent molecules in the excited-state calculations, we determine that the methanol molecules axial to the chromophore are responsible for the majority of inhomogeneous broadening, with a single methanol molecule that forms an axial hydrogen bond dominating the response. Furthermore, the strong peripheral hydrogen bonds do not contribute to spectral broadening, as they are very stable throughout the dynamics and do not lead to increased energy-gap fluctuations. We also find that treating the strong peripheral hydrogen bonds as molecular mechanical point charges during the molecular dynamics simulation underestimates the vibronic coupling. Including these peripheral hydrogen bonding methanol molecules in the quantum-mechanical region in a geometry optimization increases the vibronic coupling, suggesting that a more advanced treatment of these strongly interacting solvent molecules during the molecular dynamics trajectory may be necessary to capture the full vibronic spectral broadening.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Kubo-Anderson theory of polariton line shape

We apply the Kubo-Anderson stochastic theory of molecular spectral line shapes to the case of polaritons formed in the collective strong-coupling regime. We investigate both the fast and slow limits of the random frequency modulation of the emitter as well as the intermediate regime and show how the interplay between the characteristic timescales of the cavity and the molecular disorder is expressed in the observed polaritons line shapes. The analytical solution obtained for the slow limit is valid for any ratio between the inhomogeneous broadening of the molecules and the Rabi splitting, which is especially relevant for molecular polaritons where these two quantities can be of the same order of magnitude.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Spectral line-shape in collinear laser spectroscopy after atomic charge exchange

Collinear laser spectroscopy experiments on fast, neutral beams have been extensively used for studies on short-lived radioactive nuclei, taking advantage of its high sensitivity. The resulting resonance line-shape is known to show significant distortion, due to the energy exchange during the charge-exchange neutralization process, which can cause large systematic uncertainty in the determined centroid. A model for the line shape was constructed and simulated to be compared to measured Al, Si, and Ni hyperfine spectra. It is shown that the distortion is caused mainly by the transfer of electron into many different energy levels in the projectile atom and subsequent decays, rather than secondary inelastic collisions, which were often assumed in the line shape analysis before. Furthermore, the model can also be applied to other projectile–alkali pairs, providing a reliable line-shape with less fitting parameters than conventional phenomenological models.

Atom↗
DOE OSTI2024

PigmentHunter: A point-and-click application for automated chlorophyll-protein simulations

Chlorophyll proteins (CPs) are the workhorses of biological photosynthesis, working together to absorb solar energy, transfer it to chemically active reaction centers, and control the charge-separation process that drives its storage as chemical energy. Yet predicting CP optical and electronic properties remains a serious challenge, driven by the computational difficulty of treating large, electronically coupled molecular pigments embedded in a dynamically structured protein environment. To address this challenge, we introduce here an analysis tool called PigmentHunter, which automates the process of preparing CP structures for molecular dynamics (MD), running short MD simulations on the nanoHUB.org science gateway, and then using electrostatic and steric analysis routines to predict optical absorption, fluorescence, and circular dichroism spectra within a Frenkel exciton model. Inter-pigment couplings are evaluated using point-dipole or transition-charge coupling models, while site energies can be estimated using both electrostatic and ring-deformation approaches. The package is built in a Jupyter Notebook environment, with a point-and-click interface that can be used either to manually prepare individual structures or to batch-process many structures at once. Here, we illustrate PigmentHunter’s capabilities with example simulations on spectral line shapes in the light harvesting 2 complex, site energies in the Fenna–Matthews–Olson protein, and ring deformation in photosystems I and II.

14 SOLAR ENERGY↗
DOE OSTI2023

Impact of substrates and quantum effects on exciton line shapes of 2D semiconductors at room temperature

Exciton resonances in monolayer transition-metal dichalcogenides (TMDs) provide exceptionally strong light–matter interaction at room temperature. Their spectral line shape is critical in the design of a myriad of optoelectronic devices, ranging from solar cells to quantum information processing. However, disorder resulting from static inhomogeneities and dynamical fluctuations can significantly impact the line shape. Many recent works experimentally evaluate the optical properties of TMD monolayers placed on a substrate and the line shape is typically linked directly to the material’s quality. Here, we highlight that the interference of the substrate and TMD reflections can strongly influence the line shape. We further show how basic, room-temperature reflection measurements allow investigation of the quantum mechanical exciton dynamics by systematically controlling the substrate reflection with index-matching oils. By removing the substrate contribution with properly chosen oil, we can extract the excitonic decay rates including the quantum mechanical dephasing rate. The results provide valuable guidance for the engineering of exciton line shapes in layered nanophotonic systems.

2D semiconductor↗