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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

NASA total quality management 1989 accomplishments report

NASA and contractor employees achieved many notable improvements in 1989. The highlights of those improvements, described in this seventh annual Accomplishments Report, demonstrate that the people who support NASA's activities are getting more involved in quality and continuous improvement efforts. Their gains solidly support NASA's and this Nation's goal to remain a leader in space exploration and in world-wide market competition, and, when communicated to others through avenues such as this report, foster improvement efforts across government and industry. The principles in practice which led to these process refinements are important cultural elements to any organization's productivity and quality efforts. The categories in this report reflect NASA principles set forth in the 1980's and are more commonly known today as Total Quality Management (TQM): top management leadership and support; strategic planning; focus on the customer; employee training and recognition; employee empowerment and teamwork; measurement and analysis; and quality assurance.

Tai, Betty P.↗
NASA NTRS1990

NASA total quality management 1989 accomplishments report

Described here are the accomplishments of NASA as a result of the use of Total Quality Management (TQM). The principles in practice which led to these process refinements are important cultural elements to any organization's productivity and quality efforts. The categories of TQM discussed here are top management leadership and support, strategic planning, focus on the customer, employee training and recognition, employee empowerment and teamwork, measurement and analysis, and quality assurance.

Source record↗
NASA NTRS2006

Emerging Definition of Next-Generation of Aeronautical Communications

Aviation continues to experience rapid growth. In regions such as the United States and Europe air traffic congestion is constraining operations, leading to major new efforts to develop methodologies and infrastructures to enable continued aviation growth through transformational air traffic management systems. Such a transformation requires better communications linking airborne and ground-based elements. Technologies for next-generation communications, the required capacities, frequency spectrum of operation, network interconnectivity, and global interoperability are now receiving increased attention. A number of major planning and development efforts have taken place or are in process now to define the transformed airspace of the future. These activities include government and industry led efforts in the United States and Europe, and by international organizations. This paper will review the features, approaches, and activities of several representative planning and development efforts, and identify the emerging global consensus on requirements of next generation aeronautical communications systems for air traffic control.

Kerczewski, Robert J.↗
NASA NTRS2008

Evaluation of Vapor Pressure and Ultra-High Vacuum Tribological Properties of Ionic Liquids (2) Mixtures and Additives

Ionic liquids are salts, many of which are typically viscous fluids at room temperature. The fluids are characterized by negligible vapor pressures under ambient conditions. These properties have led us to study the effectiveness of ionic liquids containing both organic cations and anions for use as space lubricants. In the previous paper we have measured the vapor pressure and some tribological properties of two distinct ionic liquids under simulated space conditions. In this paper we will present vapor pressure measurements for two new ionic liquids and friction coefficient data for boundary lubrication conditions in a spiral orbit tribometer using stainless steel tribocouples. In addition we present the first tribological data on mixed ionic liquids and an ionic liquid additive. Post mortem infrared and Raman analysis of the balls and races indicates the major degradation pathway for these two organic ionic liquids is similar to those of other carbon based lubricants, i.e. deterioration of the organic structure into amorphous graphitic carbon. The coefficients of friction and lifetimes of these lubricants are comparable to or exceed these properties for several commonly used space oils.

Morales, Wilfredo↗
NASA NTRS2017

Asteroid Generated Tsunami Workshop: Summary of NASA/NOAA Workshop

A two-day workshop on tsunami generated by asteroid impacts in the ocean resulted in a broad consensus that the asteroid impact tsunami threat is not as great as previously thought, that airburst events in particular are unlikely to produce significant damage by tsunami, and that the tsunami contribution to the global ensemble impact hazard is substantially less than the contribution from land impacts. The workshop, led by Ethiraj Venkatapathy and David Morrison of NASA Ames, was organized into three sessions: 1) Near-field wave generation by the impact; 2) Long distance wave propagation; 3) Damage from coastal run-up and inundation, and associated hazard. Workshop approaches were to compare simulations to understand differences in the results and gain confidence in the modeling for both formation and propagation of tsunami from asteroid impacts, and to use this information for preliminary global risk assessment. The workshop focus was on smaller asteroids (diameter less than 250m), which represent the most frequent impacts.

Asteroid↗
DOE OSTI2013

Controlling the influence of Auger recombination on the performance of quantum-dot light-emitting diodes

Development of light-emitting diodes (LEDs) based on colloidal quantum dots is driven by attractive properties of these fluorophores such as spectrally narrow, tunable emission and facile processibility via solution-based methods. A current obstacle towards improved LED performance is an incomplete understanding of the roles of extrinsic factors, such as nonradiative recombination at surface defects, versus intrinsic processes, such as multicarrier Auger recombination or electron-hole separation due to applied electric field. Here we address this problem with studies that correlate the excited state dynamics of structurally engineered quantum dots with their emissive performance within LEDs. We find that because of significant charging of quantum dots with extra electrons, Auger recombination greatly impacts both LED efficiency and the onset of efficiency roll-off at high currents. Further, we demonstrate two specific approaches for mitigating this problem using heterostructured quantum dots, either by suppressing Auger decay through the introduction of an intermediate alloyed layer, or by using an additional shell that impedes electron transfer into the quantum dot to help balance electron and hole injection.

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

Three-Dimensional Modeling of the Explicit Chemistry of Organic Aerosols: Formation, Removal, and Comparison with Observations

The major goals of the project were to further our understanding of the formation of secondary organic aerosols (SOA) from major anthropogenic and biogenic precursors, and to evaluate the GECKO-A chemistry model in the context of three DOE-led field campaigns (GoAmazon, BBOP, and HI-SCALE) with the long-term objective of improving the treatment of organic gases and particles in three-dimensional regional and global models. The three field campaigns were selected to evaluate and improve specific aspects of GECKO-A: (i) GoAmazon to help quantify interactions of biogenic and anthropogenic emissions; (ii) BBOP to predict the UV-visible absorption properties of biomass burning aerosols (brown carbon) from explicit molecular properties; and (iii) HI-SCALE to evaluate new model components that include aqueous (cloud) processing of organic gases and aerosols.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Geophysical estimation of shallow permafrost distribution and properties in an ice-wedge polygon-dominated Arctic tundra region

Shallow permafrost distribution and characteristics are important for predicting ecosystem feedbacks to a changing climate over decadal to century timescales because they can drive active layer deepening and land surface deformation, which in turn can significantly affect hydrologic and biogeochemical responses, including greenhouse gas dynamics. As part of the U.S. Department of Energy Next-Generation Ecosystem Experiments- Arctic, we have investigated shallow Arctic permafrost characteristics at a site in Barrow, Alaska, with the objective of improving our understanding of the spatial distribution of shallow permafrost, its associated properties, and its links with landscape microtopography. To meet this objective, we have acquired and integrated a variety of information, including electric resistance tomography data, frequency-domain electromagnetic induction data, laboratory core analysis, petrophysical studies, high-resolution digital surface models, and color mosaics inferred from kite-based landscape imaging. The results of our study provide a comprehensive and high-resolution examination of the distribution and nature of shallow permafrost in the Arctic tundra, including the estimation of ice content, porosity, and salinity. Among other results, porosity in the top 2 m varied between 85% (besides ice wedges) and 40%, and was negatively correlated with fluid salinity. Salinity directly influenced ice and unfrozen water content and indirectly influenced the soil organic matter content. A relatively continuous but depth-variable increase in salinity led to a partially unfrozen saline layer (cryopeg) located below the top of the permafrost. The cryopeg environment could lead to year-round microbial production of greenhouse gases. Results also indicated a covariability between topography and permafrost characteristics including icewedge and salinity distribution. In addition to providing insight about the Arctic ecosystem, through integration of lab-based petrophysical results with field data, this study also quantified the key controls on electric resistivity at this Arctic permafrost site, including salinity, porosity, water content, ice content, soil organic matter content, and lithologic properties.

58 GEOSCIENCES↗
DOE OSTI2014

WE-A-BRD-01: Innovation in Radiation Therapy Planning I: Knowledge Guided Treatment Planning

Intensity modulated radiation therapy (IMRT) and Volumetric Modulated Arc Therapy (VMAT) offer the capability of normal tissues and organs sparing. However, the exact amount of sparing is often unknown until the plan is complete. This lack of prior guidance has led to the iterative, trial and-error approach in current planning practice. Even with this effort the search for patient-specific optimal organ sparing is still strongly influenced by planner's experience. While experience generally helps in maximizing the dosimetric advantages of IMRT/VMAT, there have been several reports showing unnecessarily high degree of plan quality variability at individual institutions and amongst different institutions, even with a large amount of experience and the best available tools. Further, when physician and physicist evaluate a plan, the dosimetric quality of the plan is often compared with a standard protocol that ignores individual patient anatomy and tumor characteristic variations. In recent years, developments of knowledge models for clinical IMRT/VMAT planning guidance have shown promising clinical potentials. These knowledge models extract past expert clinical experience into mathematical models that predict dose sparing references at patient-specific level. For physicians and planners, these references provide objective values that reflect best achievable dosimetric constraints. For quality assurance, applying patient-specific dosimetry requirements will enable more quantitative and objective assessment of protocol compliance for complex IMRT planning. Learning Objectives: Modeling and representation of knowledge for knowledge-guided treatment planning. Demonstrations of knowledge-guided treatment planning with a few clinical caanatomical sites. Validation and evaluation of knowledge models for cost and quality effective standardization of plan optimization.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Controlled dehumidification to extract clean water from a multicomponent gaseous mixture of organic contaminants

Rapid expansion of the unconventional oil and gas extraction has increased American energy independence, but also led to increased production of large amounts of contaminated water. Wastewater from the oil and gas industry contains a wide range of contaminants. Injecting such contaminated water into disposal wells or discharging it to the environment jeopardizes freshwater resources. Conventional and membrane-based wastewater treatment techniques are often not effective choices to treat highly contaminated wastewater; however, a suitable way to remove contaminants from wastewater is to selectively separate water in a process analogous to humidification-dehumidification (HDH). Only a few studies have investigated the use of HDH for wastewater treatment. In this study, a novel HDH system is introduced for treating highly contaminated water, such as oil and gas flowback and produced water. In this HDH process, a non-condensable gas, such as air, mixes with wastewater vapor to facilitate the separation of contaminants. As a result, clean water condenses from the multicomponent gaseous mixture while air carries organic contaminants out of the dehumidification section. A laboratory apparatus was constructed and experiments were performed to investigate the HDH process for wastewater treatment and to study the effects of flow dynamics including air flow rate on the composition of treated water. Different contaminants including benzene, toluene, 2-propanol and 2-butoxyethanol were tested. Experimental results showed that the system can be successfully applied for removing volatile and/or toxic organic contaminants from wastewater. A representative multicomponent mixture of fracking wastewater was successfully treated using the experimental setup and clean water with quality of 98.3% was obtained. It was revealed that increasing the air-to-vapor mass ratio improves purity of treated water. Quantitative analysis showed that by increasing the air-to-vapor mass ratio from 0.6 to 5.9, the fraction of separated 2-propanol through the air was improved from 43% to more than 96% of the initial amount. ASPEN software was employed to simulate equilibrium conditions. Finally, experimental results were observed to have lower mass fraction of residual contaminant in the treated water compared to equilibrium state.

42 ENGINEERING↗
DOE OSTI2023

Evaluation of Technologies for Destruction of LDR Organics in Hanford Tank Waste

Aqueous Hanford tank wastes contain soluble organics and some tanks contain small amounts (<100 mg/L) of organics that are regulated under the Land Disposal Restrictions (LDR) portions of the Resource Conservation and Recovery Act (RCRA). Most of these organics can be removed by evaporation, but some are not. Methods to destroy/remove organics that are regulated by the LDR section of the RCRA and that are not removed by evaporation may be needed if ambient temperature waste treatment processes are used to immobilize aqueous Hanford tank wastes. To identify viable and compatible organic removal or destruction pretreatment methods an evaluation was performed by a team of researchers. The team utilized a Systems Engineering Approach that examines all aspects of the technology, based on information available in the literature and the experience of the team members. That evaluation led to recommendations by the team to perform testing on technologies to determine efficacy in destroying organics in Hanford tank waste liquids. The primary technologies recommended are chemical oxidants, including permanganate, peroxymonosulfate or peroxydisulfate (PMS/PDS), hydrogen peroxide, and ozone. Ultraviolet light irradiation of the stream with a solid catalyst sorbent is also recommended for testing. A generalized description of the test program is also included.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Collaborative Research: The evolution of magnetic skeletons during 3D magnetic reconnection. Final Technical Report

The goals of this project were to investigate magnetic field evolution during 3D magnetic reconnection; begin development of an open source Python package for plasma research and education; advise students on research projects related to magnetic reconnection; and organize a conference session on diversity, equity, and inclusion in plasma physics. The principal investigator advanced an analytical theory to describe the ideal and non-ideal motion of the magnetic field lines that connect two magnetic null points; led development of the PlasmaPy package through version 0.2.0; directly advised two students; and is co-organizing a town hall on diversity, equity, and inclusion at a major plasma physics conference.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Leptothrix ochracea genomes reveal potential for mixotrophic growth on Fe(II) and organic carbon

ABSTRACT Leptothrix ochracea creates distinctive iron-mineralized mats that carpet streams and wetlands. Easily recognized by its iron-mineralized sheaths, L. ochracea was one of the first microorganisms described in the 1800s. Yet it has never been isolated and does not have a complete genome sequence available, so key questions about its physiology remain unresolved. It is debated whether iron oxidation can be used for energy or growth and if L. ochracea is an autotroph, heterotroph, or mixotroph. To address these issues, we sampled L. ochracea -rich mats from three of its typical environments (a stream, wetlands, and a drainage channel) and reconstructed nine high-quality genomes of L. ochracea from metagenomes. These genomes contain iron oxidase genes cyc2 and mtoA, showing that L. ochracea has the potential to conserve energy from iron oxidation. Sox genes confer potential to oxidize sulfur for energy. There are genes for both carbon fixation (RuBisCO) and utilization of sugars and organic acids (acetate, lactate, and formate). In silico stoichiometric metabolic models further demonstrated the potential for growth using sugars and organic acids. Metatranscriptomes showed a high expression of genes for iron oxidation; aerobic respiration; and utilization of lactate, acetate, and sugars, as well as RuBisCO, supporting mixotrophic growth in the environment. In summary, our results suggest that L. ochracea has substantial metabolic flexibility. It is adapted to iron-rich, organic carbon-containing wetland niches, where it can thrive as a mixotrophic iron oxidizer by utilizing both iron oxidation and organics for energy generation and both inorganic and organic carbon for cell and sheath production. IMPORTANCE Winogradsky's observations of L. ochracea led him to propose autotrophic iron oxidation as a new microbial metabolism, following his work on autotrophic sulfur-oxidizers. While much culture-based research has ensued, isolation proved elusive, so most work on L. ochracea has been based in the environment and in microcosms. Meanwhile, the autotrophic Gallionella became the model for freshwater microbial iron oxidation, while heterotrophic and mixotrophic iron oxidation is not well-studied. Ecological studies have shown that Leptothrix overtakes Gallionella when dissolved organic carbon content increases, demonstrating distinct niches. This study presents the first near-complete genomes of L. ochracea , which share some features with autotrophic iron oxidizers, while also incorporating heterotrophic metabolisms. These genome, metabolic modeling, and transcriptome results give us a detailed metabolic picture of how the organism may combine lithoautotrophy with organoheterotrophy to promote Fe oxidation and C cycling and drive many biogeochemical processes resulting from microbial growth and iron oxyhydroxide formation in wetlands.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

Compilation of PRF Canyon Floor Pan Sample Analysis Results

On September 28, 2015, debris collected from the PRF (236-Z) canyon floor, Pan J, was observed to exhibit chemical reaction. The material had been transferred from the floor pan to a collection tray inside the canyon the previous Friday. Work in the canyon was stopped to allow Industrial Hygiene to perform monitoring of the material reaction. Canyon floor debris that had been sealed out was sequestered at the facility, a recovery plan was developed, and drum inspections were initiated to verify no additional reactions had occurred. On October 13, in-process drums containing other Pan J material were inspected and showed some indication of chemical reaction, limited to discoloration and degradation of inner plastic bags. All Pan J material was sealed back into the canyon and returned to collection trays. Based on the high airborne levels in the canyon during physical debris removal, ETGS (Encapsulation Technology Glycerin Solution) was used as a fogging/lock-down agent. On October 15, subject matter experts confirmed a reaction had occurred between nitrates (both Plutonium Nitrate and Aluminum Nitrate Nonahydrate (ANN) are present) in the Pan J material and the ETGS fixative used to lower airborne radioactivity levels during debris removal. Management stopped the use of fogging/lock-down agents containing glycerin on bulk materials, declared a Management Concern, and initiated the Potential Inadequacy in the Safety Analysis determination process. Additional drum inspections and laboratory analysis of both reacted and unreacted material are planned. This report compiles the results of many different sample analyses conducted by the Pacific Northwest National Laboratory on samples collected from the Plutonium Reclamation Facility (PRF) floor pans by the CH2MHill’s Plateau Remediation Company (CHPRC). Revision 1 added Appendix G that reports the results of the Gas Generation Rate and methodology. The scope of analyses requested by CHPRC includes the determination of common anions, gamma spectrometry, metals, corrosivity, organics and alpha spectrometry (note: alpha spectrometry was cancelled during the performance of this work with concurrence from CHPRC). Results may help elucidate the components that led to the unexpected reaction in the canyon as well as inform the radiological and hazardous characteristics. The specific anions, gamma emitters, organics and metals requested by CHPRC are provided in the analytical reports sections. The individual analyses were conducted under the Plutonium Finishing Plant (PFP) Floor Pan Evaluation Project Quality Assurance Project Plan (PFP Floor Pan Evaluation QAPP, Revision 0.) developed by PNNL specifically for this project. The final reports for each analysis set are included in this compilation of the results. Each package was reviewed under the PFP Floor Pan Evaluation Project Quality Assurance Project Plan so no additional reviews were conducted in this compilation task. The Gas Generation Rates in Appendix G were conducted under the PNNL “How Do I…” quality assurance program and were NOT conducted under the Plutonium Finishing Plant (PFP) Floor Pan Evaluation Project Quality Assurance Project Plan (PFP Floor Pan Evaluation QAPP, Revision 0.).

36 MATERIALS SCIENCE↗
NASA NTRS1991

The 1991 International Conference on Aging Aircraft and Structural Airworthiness

Civil aviation serves a strategic interest to the United States. Thus, the need to maintain a high standard of aviation safety is axiomatic. While the industry has witnessed phenomenal growth in the past two decades, the proportion of aging aircraft in air carrier fleets has been ever increasing-a trend that is projected to continue. Certain events which occurred in 1988 and previous years and public concern about the safety of the high time aircraft led to an International Conference on Aging Aircraft in Washington, D.C., during which a number of aviation safety related issues applicable to aging aircraft were raised and discussed among the conference participants. Various groups that have a vital stake in commercial aviation made certain recommendations which led to the formation of a task force and a broad undertaking involving the Federal Aviation Administration (FAA), the National Aeronautics and Space Administration (NASA), industry and international organizations to insure continued airworthiness of aging airplanes. At the same time, significant research and development programs were initiated by the FAA and NASA to complement the broader effort. In view of the success of the 1988 conference, the FAA desired that conferences be held annually to disseminate information on the status of the task force's activities on aircraft certification and airline maintenance related issues and to offer a forum for participation by all interested parties. Thus, the 2nd International Conference was held in 1989 in Baltimore and the third in the series in 1990 in Bordeaux, France. Both of them, like the first conference, attracted rousing attendance and interest. Thus, the stage was set for organizing the 4th International Conference in 1991. By 1991, the FAA and NASA research programs were yielding significant results, a consideration that led to a larger segment of the 4th International Conference Program being devoted to presentations about the impact of the research on the other activities of the task group. Agreement had also been reached between the FAA and NASA to coordinate and integrate their respective program activities. Hence, NASA was co-opted as a sponsor of the conference. A group consisting of Mr. Stephen Erickson of the Air Transport Association of America, Mr. Jesse Lewis and Mr. Richard Johnson of the FAA, and Mr. Thomas Crooker of NASA was formed to organize the conference. The members of the group are owed special thanks for their efforts that ensured the success of the conference.

Aging Aircraft↗
DOE OSTI2015

Synthesis and photoluminescence properties of Dy{sup 3+} doped white light emitting CdTa{sub 2}O{sub 6} phosphors

The undoped and CdTa{sub 2}O{sub 6}:Dy{sup 3+} (0.2≤x≤2.0 mol%) phosphors were synthesized at 1100 °C for 12 h by the conventional solid state reaction method. The synthesized CdTa{sub 2}O{sub 6}:Dy{sup 3+} phosphors were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS) and Photoluminescence (PL) analyses. The PL spectra showed the presence of excitation peaks between 310 and 440 nm due to the 4f–4f transitions of Dy{sup 3+}. The emission of Dy{sup 3+} ions at 353.0 nm excitation was observed at 487.1 nm (blue) and 577.8 nm (yellow) due to the {sup 4}F{sub 9/2}→{sup 6}H{sub 15/2} transitions and {sup 4}F{sub 9/2}→{sup 6}H{sub 13/2} transitions, respectively. The PL analysis results also showed that the emissions increase with the increasing Dy{sup 3+} ion content. The emissions increased with the doping concentration of up to 1 mol%, and above this level decreased due to concentration quenching effect. The CIE chromaticity color coordinates (x,y) of the CdTa{sub 2}O{sub 6}:Dy{sup 3+} phosphors were found to be in the white light region of the chromaticity diagram. - Graphical abstract: Emission spectra at λ{sub ex}=353.0 nm and CIE chromaticity coordinate diagram of CdTa{sub 2}O{sub 6}:Dy{sup 3+} phosphors. - Highlights: • Pure and CdTa{sub 2}O{sub 6}:Dy{sup 3+} was produced by solid state reaction method. • CdTa{sub 2}O{sub 6}:Dy{sup 3+} phosphor exhibited blue and yellow emissions due to the {sup 4}F{sub 9/2}→{sup 6}H{sub 15/2} and {sup 4}F{sub 9/2}→{sup 6}H{sub 13/2} transitions. • The CCT value for 1.0 mol% CdTa{sub 2}O{sub 6}:Dy{sup 3+} was 5133 K which was located in the cool white daylight region. • Dy{sup 3+} doped CdTa{sub 2}O{sub 6} phosphor has potential in the production of white LEDs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

High-Performance Blue-Excitable Yellow Phosphor Obtained from an Activated Solvochromic Bismuth-Fluorophore Metal–Organic Framework

Here, we report the synthesis, structure, and photoluminescence properties of a new bismuth based luminescent metal-organic framework (LMOF). The framework is comprised of a 9-coordinated Bi 3+ building unit and 4', 4''', 4''''', 4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis([1,1'-biphenyl]-4-carboxylic acid) (H 4 tcbpe) organic linker, which has strong yellow aggregation induced emission (AIE). The structure can be viewed as two interpenetrated 4,4-anionic nets that are stabilized by K + ions forming one-dimensional helical inorganic chains by connecting bismuth nodes through shared oxygen bonds. The as-made LMOF has a bluish emission centered at 459 nm with an internal quantum yield of 57% when excited at 360 nm. The emission properties of the LMOF were found to be highly solvochromic with respect to DMF. Upon partial solvent removal, the framework undergoes significant red-shifting to a greenish emission centered at 500 nm. Complete removal of DMF results in additional red-shifting fluorescence coupled with structural changes. The resulting material has strong blue-excitable (455 nm) yellow emission centered at 553 nm, with a quantum yield of 74%, which is maintained after heating in air for 5 days at 90°C. This is the second highest quantum yield value for blue-excited yellow emission among all reported LMOFs.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Deactivating Emission in Azulene via Solvent-Induced (Anti)Aromaticity

Anti-Kasha emission is a coveted feature in optoelectronics, with promise in areas such as imaging, sensing, and the production of white-light LEDs via dual-photon emission. Despite being a rare feature in organic systems, anti-Kasha emission is readily observed in the deceptively simple molecule azulene, which possesses two bright singlet states in the UV–visible spectrum and readily emits from the S 2 state. With dominant anti-Kasha emission and decades of synthetic study, azulene is a perfect candidate for novel material fabrication; however, large gaps persist in understanding the photophysics of even the simple parent compound. These range from competing, experimentally unverified models of azulene reactivity and aromaticity to the unexplained deactivation of anti-Kasha emission in a host of azulene derivatives. Herein, we use fluorescence and transient absorption spectroscopies to explore the detailed solvent dependence of azulene photophysics. We discover a tunable reduction in the S 2 lifetime via weak complexation with aromatic solvents. Interestingly, our results are independent of polarity, highlighting the primacy of peripherally delocalized 10-π Hückel aromaticity over zwitterionic character. When the dipolar character is enhanced through chemical functionalization, we observe even greater sensitivity to solvent aromaticity and more rapid quenching, revealing the role of conical intersections in azulenes with zwitterionic excited states. Overall, this work provides essential mechanistic insight into the photophysics of azulene and reveals a simple new approach to control the excited-state aromaticity and anti-Kasha emission in this class of materials.

Absorption↗