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Results for “Stokes shift”

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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15 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

(NH 3 (CH 2 ) 7 NH 3 ) 2 Sn 3 I 10 , a Vacancy-Ordered Three-Dimensional Tin(II) Perovskite-Derived Semiconductor

Ordering vacancies in hybrid Sn(II) halide semiconductors provides a strategy for preventing uncontrolled oxidation and formation of mobile holes. In this study, we report the structure and optical and electronic properties of (NH 3 (CH 2 ) 7 NH 3 ) 2 Sn 3 I 10 , a vacancy-ordered perovskite derivative with three-dimensional inorganic connectivity. The crystal structure resembles that of a Dion–Jacobson layered perovskite derivative, but with [SnI 5 ] square pyramids bridging the layers. UV–vis diffuse reflectance spectroscopy reveals a sharp onset of light absorption at 1.86(1) eV with the photoluminescence emission maximum at 1.90(1) eV. However, the maximum excitation occurs from 3.42 to 3.81 eV (325 to 370 nm), revealing a significant Stokes shift of 1.3 eV. The electronic properties determined from dark and time-resolved microwave conductivity measurements reveal a minimum carrier mobility of 4.3 × 10 –2 cm 2 V –1 s –1 and a maximum carrier density of 5.96 × 10 16 cm –3 , a uniquely low value for a hybrid Sn(II) halide semiconductor. The transport behavior in combination with first-principles calculations of the electronic band structure and dielectric permittivity suggest polaron-mediated electronic transport, yet the photogenerated carriers have a fast and fluence-dependent nonradiative recombination rate, suggestive of localized “defect-like” states at the band edge. The observed photoluminescence is most consistent with single-ion-like behavior of an asymmetric Sn(II) environment. Together, these results suggest that defect ordering presents a strategy for the reduction of mobile charge carriers at equilibrium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Excited-state vibronic coherences and intramolecular charge transfer dynamics of the photoinactive cyanobacteriochrome NpF2164g5

We have characterized the excited-state structural dynamics that follow optical excitation of the photoinactive cyanobacteriochrome (CBCR) NpF2164g5 to determine the first events along the photoisomerization reaction coordinate of the phycocyanobilin (PCB) chromophore in red-to-green photoactive CBCRs. Within 25 fs of photoexcitation to the first excited singlet state, S1, a cross peak begins to develop below the diagonal of the broadband two-dimensional electronic spectrum (2DES) owing to the formation of a twisted conformation of the PCB chromophore with an enhanced intramolecular charge-transfer (ICT) character. Excited-state coherent wavepacket motions, including a torsion of the methine bridge between rings C and D and the carbon–hydrogen out-of-plane (HOOP) wagging vibration, are rapidly damped as the cross peak forms. This finding supports an assignment of the torsional and HOOP modes to the reaction coordinate of a coherent nonadiabatic mechanism. The ICT process is accompanied by an ultrafast Stokes shift and rapidly damped oscillations at the torsional mode’s frequency, which are sensed by measurements of the energy gap of the cross peak using its first moment with respect to the detection frequency axis of the 2DES spectrum. Furthermore, these results have the further implication that polar side chains of nearby amino acid residues in the binding site of the PCB chromophore can manipulate the barrier height for photoisomerization in red-to-green photoactive CBCRs and in phytochromes by redistributing the π-electron density along the methine bridge between the C and D rings.

Charge transfer↗
DOE OSTI2025

Substituent effect on napthodithiophene-fused porphyrins: Understanding the unusual trend of fluorescence quantum yield quenching

A series of π-extended porphyrins containing thiophene units was prepared to investigate an unusual trend observed in the fluorescence quantum yield of naphtho[2,1-b:3,4-b']dithiophene-fused porphyrins. Monobenzoporphyrins carrying 2-thiophenyl (vinyl thiophene porphyrin) groups (2VTP, 2VTBr and Br2VTP) (numbering 2 and 3 refers to the position of sulfur on the thiophene ring) were synthesized through a Heck-based cascade reaction followed by a newly developed bromination method. These were converted to naphtho[2,1-b:3,4-b']dithiophene-fused porphyrin derivatives (FBr2VTP and F2VTBr) via ring closure with an intramolecular Scholl reaction. Increasingly larger Stokes shifts with a higher number of bromo groups were observed in the unfused π-extended molecular systems, reflecting the heavy atom effect. Fluorescence spectroscopy further confirmed the unusual trend seen in the previous work: structural rigidification in naphtho[2,1-b:3,4-b']dithiophene-fused porphyrins leads to longer fluorescence lifetimes but unexpectedly lowers the quantum yield. Adding one bromo group to the naphtho[2,1-b:3,4-b']dithiophene unit does not change this trend. Furthermore, the presence of two bromo groups prevents the quantum yield from dropping. DFT, TDDFT, and NICS analyses suggest a drastic change in aromaticity in the pyrrole ring where the naphtho[2,1-b:3,4-b']dithiophene is fused in FBr2VTP, which might contribute to the quantum yield reductions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Low-Threshold Visible-to-Ultraviolet Solid-State Triplet-Fusion Upconversion

Visible-to-ultraviolet (UV) triplet-triplet annihilation (TTA) upconversion is an energy-relevant photon-management strategy that converts visible photons into UV photons capable of driving high-energy photochemical processes. Practical implementation requires solid-state thin films, which often require high excitation power. Here, we demonstrate the first solid-state visible-to-UV TTA upconversion thin-film device, using 1,4-bis((tricyclopentylsilyl)ethynyl)naphthalene (TCPS-NAP) as the annihilator and tris(2-phenylpyridine)iridium(III) (Ir(ppy) 3 ) as the sensitizer on silver. Under incoherent 455 nm excitation, the device exhibits blue-to-UV upconversion with a threshold of 4.8 mW/cm 2 . Using surface plasmons in the planar silver film, we achieve green-to-UV upconversion with a 1.11 eV anti-Stokes shift and 6.9 mW/cm 2 threshold, a 12.2 × threshold enhancement over far-field 532 nm excitation. In solution, TCPS-NAP shows excimer-dominated anti-Stokes emission rather than UV upconversion. These results establish a platform for harvesting low-intensity visible light to drive UV processes while demonstrating that solution-phase screening does not predict solid-state upconversion performance.

Luminescence↗
DOE OSTI2026

Highly Anisotropic Quasi‐Direct Organic Metal Halide Hybrids: A Platform for Polarization‐Sensitive Optoelectronics

Low-dimensional organic–inorganic metal halide hybrids (OMHHs) exhibit remarkable optical properties and enhanced environmental stability. We investigate a 1D OMHH with formula C 4 N 2 H 14 PbBr 4 , consisting of Pb–Br chains separated by organic cations, which shows a large Stokes shift (0.83 eV) and broadband emission. Through first-principles calculations and polarized Raman spectroscopy, we characterize the material's vibrational properties and identify the specific phonon modes that drive exciton self-trapping. Our novel GW/Bethe-Salpeter equation force formalism reveals that low-frequency phonons (∼ 100 cm −1 , primarily involving Pb–Br motions) couple strongly with excitons, with a remarkably high Huang-Rhys factor of 137 ± 4, and gives a pathway for ultrafast structural analysis during the absorption process. This phonon-exciton coupling mechanism explains the material's broadband emission and provides a pathway for controlling optical properties through vibrations and for tuning vibrations through optical excitations. The material also exhibits highly anisotropic optical properties and electronic transport, with bands that are dispersive along the Pb–Br chains but nearly flat in perpendicular directions, resulting in direction-dependent electrical conductivity that is calculated to be an order of magnitude higher along the chain direction and consistent with measurements. These combined properties make this system an excellent platform for polarization-sensitive optoelectronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Effects of Quantum Dot Loading on the Radioluminescence Efficiency in Quantum-Dot-Embedded Composites

Nanoparticle-embedded plastic scintillators are an emerging technology for fast, large-area, high-resolution radiation detection and imaging. Here, this study investigates the properties of such composites, focusing on the effects of the quantum dot (QD) concentration on the radioluminescence (RL) intensity, spectra, and dynamics. Experiments using CdSe/CdS QDs in a polymer reveal a superlinear increase in RL with the QD concentration despite optical losses from inner filtering and interparticle interactions. When corrected for inner filtering, RL shows a quadratic concentration dependence, consistent with simple analytical models of improving the secondary electron capture. Practically, the benefits of high QD concentrations are muted by optical losses, but the findings apply to other systems with insulating hosts. In addition to manipulating emission for large effective Stokes shifts, future improvements may come from hosts with higher stopping power and better charge transport, which enable more effective funneling of excitations but without concomitant optical losses associated with high nanoparticle concentrations.

Auger recombination↗
DOE OSTI2026

Plasmons Enable Ultralow Threshold Solid-State Triplet Fusion Upconversion with a 2D Sensitizer

Solid-state triplet−triplet annihilation (TTA) upconversion has significant potential for application in light harvesting, optoelectronic devices, and bioimaging. However, the high optical powers required to achieve efficient upconversion have inhibited its adoption. In this work, we demonstrate plasmon-enhanced near-infrared (NIR)-to-blue TTA upconversion in a monolayer WSe2/organic heterojunction. Under far-field excitation, the device reaches a threshold of 19 mW/cm 2 and an external quantum efficiency (EQE) of 0.17% with an anti-Stokes shift of 1.1 eV. Plasmon excitation lowers the threshold to 0.9 mW/cm 2 and improves the EQE to 3.6%. We attribute the plasmon enhancement to surface plasmon polariton (SPP) near-field enhancement and dark-exciton absorption. Optimization of the WSe 2 transfer process is identified as a key factor for the device performance. This work demonstrates that plasmon excitation overcomes the low far-field absorption of 2D transition-metal dichalcogenide (TMD) sensitizers. Consequently, monolayer TMDs can achieve solid-state upconversion with a performance among the best reported.

2D materials↗
DOE OSTI2025

Impact of hole polaron formation on excitonic transitions in MgO from first principles

Here, we present a first-principles investigation of the excitonic properties of magnesia (MgO), an ionic insulator known to host hole polarons. We combine a density functional theory-based approach for structural relaxation in the presence of the hole and many-body perturbation theory to describe the excitonic properties. We determine that the hole polaron introduces new in-gap occupied states 0.6–0.8 eV above the valence band maximum that lead to two low-energy peaks in the optical spectrum. The predicted redshift of the lowest-energy transition due to polaron formation of 0.8 eV agrees well with the experimental Stokes shift of 0.8–0.9 eV. Analysis of the exciton wave function indicates that the electron-hole pair consists of a localized hole and delocalized electron, but that the wave function retains its Wannier-Mott character even in the presence of the hole polaron. Our study demonstrates that combining these previously established methods allows for a relatively computationally inexpensive approach to studying the exciton polaron in materials where only one charge carrier forms a polaron.

electronic structure↗
DOE OSTI2025

Database of low‐temperature absorption and fluorescence spectra of native photosynthetic tetrapyrrole macrocycles

Low-temperature (77 K) absorption and fluorescence spectra of 12 naturally occurring photosynthetic tetrapyrrole macrocycles have been recorded in a frozen glass (2-methyltetrahydrofuran). The compounds encompass distinct chromophore classes: porphyrin, chlorophyll c 2 ; chlorin, chlorophylls a, b, d, f and bacteriochlorophylls c, d, e, f; and bacteriochlorin, bacteriochlorophylls a, b, g. The spectra are compared with those of the same pigment in liquid solution (predominantly 2-methyltetrahydrofuran) at room temperature (293 K). The measured Stokes shifts at 77 K across the 12 macrocycles range from ~30 to 300 cm −1 . The spectral data in digital form are made available as part of the PhotochemCAD databases. Literature searches have revealed extensive published data for Chl a (often in biological matrices) but at best rather limited data for less common macrocycles. The availability of a systematic collection of curated spectral data collected at low temperature should be useful for a variety of assessments, including reconstruction of absorption spectra of (bacterio)chlorophyll-containing protein complexes, vibrational analysis of absorption and fluorescence spectra, and calculations where knowledge of energy levels is important.

Niedzwiedzki, Dariusz M. [Washington University in↗
DOE OSTI2025

Analysis of the weighted shifted boundary method for the Poisson and Stokes problems

The Shifted Boundary Method (SBM) belongs to the class of unfitted (or immersed, or embedded) finite element methods, and relies on reformulating the original boundary value problem over a surrogate (approximate) computational domain. Accuracy is maintained by properly shifting the location and values of the boundary conditions. This avoids integration over cut cells and the associated implementation issues. Recently, the Weighted SBM (WSBM) was proposed for the Navier-Stokes equations with free surfaces and the Stokes flow with moving boundaries. The attribute “weighted” in the name WSBM stems from the fact that its variational form is weighted with the elemental volume fraction of active fluid. The motivation for the development of the WSBM was the preservation of the volume of active fluid to a higher degree of accuracy, which in turn resulted in improved stability and robustness characteristics in moving-boundary, time-dependent simulations. In this article, we present the numerical analysis of the WSBM formulations for the Poisson and Stokes problems. We give mathematical conditions under which the bilinear forms defining the discrete variational formulations are uniformly coercive (Poisson problem) or inf-sup stable (Stokes problem). By these results, stability and optimal convergence is proven in the natural norm; L2-error estimates can also be derived.

Approximate domain boundaries↗
DOE OSTI2026

Thomson Scattering with Gain

Thomson-scattering signals can be significantly modified by convective gains associated with the stimulated Raman scattering and stimulated Brillouin scattering instabilities as the scattered light traverses the probe beam. Gain results in amplification and narrowing of the red-shifted (i.e., Stokes) scattered light, whereas blue-shifted (anti-Stokes) features are depleted and broadened, making the relative prominence of these features a key signature of gain. Not accounting for instability growth has been a ubiquitous source of error in previous Thomson-scattering measurements.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Non-equilibrium anti-Stokes Raman spectroscopy for investigating Higgs modes in superconductors

Abstract Even before its role in electroweak symmetry breaking, the Anderson-Higgs mechanism was introduced to explain the Meissner effect in superconductors. Spontaneous symmetry-breaking yields massless phase modes representing the low-energy excitations of the Mexican-Hat potential. Only in superconductors the phase mode is shifted towards higher energies owing to the gauge field of the charged condensate. This results in a low-energy excitation spectrum governed by the Higgs mode. Consequently, the Bardeen-Cooper-Schrieffer-like Meissner effect signifies a macroscopic quantum condensate in which a photon acquires mass, representing a one-to-one analogy to high-energy physics. We report on an innovative spectroscopic technique to study symmetries and energies of the Higgs modes in the high-temperature superconductor Bi 2 Sr 2 CaCu 2 O 8 after a soft quench of the Mexican-Hat potential. Population inversion induced by an initial laser pulse leads to an additional anti-Stokes Raman-scattering signal, which is consistent with polarization-dependent Higgs modes. Within Ginzburg-Landau theory, the Higgs-mode energy is connected to the Cooper-pair coherence length. Within a Bardeen-Cooper-Schrieffer weak-coupling model we develop a quantitative and coherent description of single-particle and two-particle channels. This opens the avenue for Higgs Spectroscopy in quantum condensates and provides a unique pathway to control and explore Higgs physics.

Science & Technology - Other Topics↗
DOE OSTI2024

Self-assembled reconfigurable pump architectures via magnetic colloidal swarms

Self-assembled swarms of interactive active units, which are adaptive and dynamically reconfigurable to accommodate different functionalities, represent a promising platform for the development of next-generation robotics. Here, we utilize the emergent collective behavior of active magnetic colloids confined in quasi-two-dimensional arrays of overlapping wells to demonstrate the self-organization of a colloidal swarm into a dynamic pump architecture capable of controlled transport of passive cargo particles. This dynamic architecture provides a global unidirectional looping flow pattern along the entire length of the system. We show that the flow direction of the dynamic swarm-based pump can be externally controlled by a phase shift of a driving magnetic field energizing the swarm. The experimental observations are supported by computational modeling based on phenomenological coarse-grained particle dynamics coupled to shallow-water Navier-Stokes hydrodynamics. In conclusion, our findings demonstrate how the emergent collective behavior of a swarm can be orchestrated into a desired functionality by exploiting the interplay between activity and confinement potentials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

The Impact of Clean Grid Transition on Wastewater Sector Greenhouse Gas Emissions

This study examines the spatial and temporal impacts of the U.S. clean energy grid transition on related greenhouse gas (GHG) emissions from the wastewater treatment industry. By analyzing data from 17,156 water resource recovery facilities (WRRFs) and state-specific grid decarbonization scenarios, the results project a 60% reduction in Scope 2 emissions by 2050, driven by the national shift to renewable energy. However, regional disparities are prominent, with northeastern and western states achieving the most significant reductions, while the Ohio Valley and Rockies are likely to experience higher emissions due to the reliance on fossil fuels. This study offers the first assessment of clean grid impacts on the WRRFs and highlights the need for targeted, region-specific strategies across different emission scopes. This research provides insights for policymakers and stakeholders in the wastewater sector, emphasizing the critical role of grid decarbonization in achieving GHG reduction goals.

Li, Xiatong↗