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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
NASA NTRS2009

SDBI 1904: Human Factors Assessment of Vibration Effects on Visual Performance during Launch

The primary objective of the of Human Factors Short Duration Bioastronautics Investigation (SDBI) 1904 is to determine visual performance limits during operational vibration and g-loads, specifically through the determination of minimal usable font sizes using Orion-type display formats. Currently there is little to no data available to quantify human visual performance under these extreme conditions. Existing data on shuttle vibration magnitude and frequency is incomplete, does not address seat and crew vibration in the current configuration, and does not address human visual performance. There have been anecdotal reports of performance decrements from shuttle crews, but no structured data has been collected. The SDBI is a companion effort to the Detailed Test Objective (DTO) 695, which will measure shuttle seat accelerations (vibration) during ascent. Data from the SDBI will serve an important role in interpreting the DTO vibration data. This data will be collected during the ascent phase of three shuttle missions (STS-119, 127, and 128). Both SDBI1904 and DTO 695 are low impact with respect to flight resources, and combined they represent an efficient and focused problem solving approach. The SDBI and DTO data will be correlated to determine the nature of perceived visual performance under varying vibrations and g-loads. This project will provide: * Immediate data for developing preliminary human performance vibration requirements * Flight validated inputs for ongoing and future ground-based research * Information of functional needs that will drive Orion display format design decisions

Shelby G Thompson↗
NASA NTRS2010

Random Vibrations

Ares I Zonal Random vibration environments due to acoustic impingement and combustion processes are develop for liftoff, ascent and reentry. Random Vibration test criteria for Ares I Upper Stage pyrotechnic components are developed by enveloping the applicable zonal environments where each component is located. Random vibration tests will be conducted to assure that these components will survive and function appropriately after exposure to the expected vibration environments. Methodology: Random Vibration test criteria for Ares I Upper Stage pyrotechnic components were desired that would envelope all the applicable environments where each component was located. Applicable Ares I Vehicle drawings and design information needed to be assessed to determine the location(s) for each component on the Ares I Upper Stage. Design and test criteria needed to be developed by plotting and enveloping the applicable environments using Microsoft Excel Spreadsheet Software and documenting them in a report Using Microsoft Word Processing Software. Conclusion: Random vibration liftoff, ascent, and green run design & test criteria for the Upper Stage Pyrotechnic Components were developed by using Microsoft Excel to envelope zonal environments applicable to each component. Results were transferred from Excel into a report using Microsoft Word. After the report is reviewed and edited by my mentor it will be submitted for publication as an attachment to a memorandum. Pyrotechnic component designers will extract criteria from my report for incorporation into the design and test specifications for components. Eventually the hardware will be tested to the environments I developed to assure that the components will survive and function appropriately after exposure to the expected vibration environments.

Messaro. Semma↗
NASA NTRS2011

Shunted Piezoelectric Vibration Damping Analysis Including Centrifugal Loading Effects

Excessive vibration of turbomachinery blades causes high cycle fatigue problems which require damping treatments to mitigate vibration levels. One method is the use of piezoelectric materials as passive or active dampers. Based on the technical challenges and requirements learned from previous turbomachinery rotor blades research, an effort has been made to investigate the effectiveness of a shunted piezoelectric for the turbomachinery rotor blades vibration control, specifically for a condition with centrifugal rotation. While ample research has been performed on the use of a piezoelectric material with electric circuits to attempt to control the structural vibration damping, very little study has been done regarding rotational effects. The present study attempts to fill this void. Specifically, the objectives of this study are: (a) to create and analyze finite element models for harmonic forced response vibration analysis coupled with shunted piezoelectric circuits for engine blade operational conditions, (b) to validate the experimental test approaches with numerical results and vice versa, and (c) to establish a numerical modeling capability for vibration control using shunted piezoelectric circuits under rotation. Study has focused on a resonant damping control using shunted piezoelectric patches on plate specimens. Tests and analyses were performed for both non-spinning and spinning conditions. The finite element (FE) shunted piezoelectric circuit damping simulations were performed using the ANSYS Multiphysics code for the resistive and inductive circuit piezoelectric simulations of both conditions. The FE results showed a good correlation with experimental test results. Tests and analyses of shunted piezoelectric damping control, demonstrating with plate specimens, show a great potential to reduce blade vibrations under centrifugal loading.

Min, James B.↗
NASA NTRS2003

Viscoelastic Vibration Dampers for Turbomachine Blades

Simple viscoelastic dampers have been invented for use on the root attachments of turbomachine blades. These dampers suppress bending- and torsion-mode blade vibrations, which are excited by unsteady aerodynamic forces during operation. In suppressing vibrations, these dampers reduce fatigue (thereby prolonging blade lifetimes) while reducing noise. These dampers can be installed in new turbomachines or in previously constructed turbomachines, without need for structural modifications. Moreover, because these dampers are not exposed to flows, they do not affect the aerodynamic performances of turbomachines. Figure 1 depicts a basic turbomachine rotor, which includes multiple blades affixed to a hub by means of dovetail root attachments. Prior to mounting of the blades, thin layers of a viscoelastic material are applied to selected areas of the blade roots. Once the blades have been installed in the hub and the rotor is set into rotation, centrifugal force compresses these layers between the mating load-bearing surfaces of the hub and the blade root. The layers of viscoelastic material provide load paths through which the vibration energy of the blade can be dissipated. The viscoelasticity of the material converts mechanical vibration energy into shear strain energy and then from shear strain energy to heat. Of the viscoelastic materials that have been considered thus far for this application, the one of choice is a commercial polyurethane that is available in tape form, coated on one side with an adhesive that facilitates bonding to blade roots. The thickness of the tape can be chosen to suit the specific application. The typical thickness of 0.012 in. (.0.3 mm) is small enough that the tape can fit in the clearance between the mating blade-root and hub surfaces in a typical turbomachine. In an experiment, a blade was mounted in a test fixture designed to simulate the blade-end conditions that prevail in a turbocompressor. Vibrations were excited in the blade by use of an impact hammer, and damping of the vibrations was measured by use of a dynamic signal analyzer. Tests were performed without and with viscoelastic dampers installed in the dovetail root attachment. The results of the measurements, some of which are presented in Figure 2, show that the viscoelastic dampers greatly increased the rate of damping of vibrations. Accordingly, dynamic stresses on rotor blades were significantly reduced, as shown in Figure 2.

Nguyen, Nhan↗
NASA NTRS2012

Vibration Propagation of Gear Dynamics in a Gear-Bearing-Housing System Using Mathematical Modeling and Finite Element Analysis

Vibration and noise caused by gear dynamics at the meshing teeth propagate through power transmission components to the surrounding environment. This study is devoted to developing computational tools to investigate the vibro-acoustic propagation of gear dynamics through a gearbox using different bearings. Detailed finite element/contact mechanics and boundary element models of the gear/bearing/housing system are established to compute the system vibration and noise propagation. Both vibration and acoustic models are validated by experiments including the vibration modal testing and sound field measurements. The effectiveness of each bearing type to disrupt vibration propagation is speed-dependent. Housing plays an important role in noise radiation .It, however, has limited effects on gear dynamics. Bearings are critical components in drivetrains. Accurate modeling of rolling element bearings is essential to assess vibration and noise of drivetrain systems. This study also seeks to fully describe the vibro-acoustic propagation of gear dynamics through a power-transmission system using rolling element and fluid film wave bearings. Fluid film wave bearings, which have higher damping than rolling element bearings, could offer an energy dissipation mechanism that reduces the gearbox noise. The effectiveness of each bearing type to disrupt vibration propagation in explored using multi-body computational models. These models include gears, shafts, rolling element and fluid film wave bearings, and the housing. Radiated noise is mapped from the gearbox surface to surrounding environment. The effectiveness of rolling element and fluid film wave bearings in breaking the vibro-acoustic propagation path from the gear to the housing is investigated.

Parker, Robert G.↗
NASA NTRSDate not supplied

Modal Test and Model Correlation of NASA Plum Brook Station Mechanical Vibration Facility Head Expander –Lessons Learned from the Perspective of an Early-Career Engineer

In preparation for the Sierra Nevada Corporation’s (SNC) Dream Chaser spacecraft vibration test campaign at the Mechanical Vibration Facility (MVF) at NASA Plum Brook Station (PBS) in Sandusky, Ohio, a test-verified model of MVF is needed in order to be able to perform accurate pretest analysis used for determining response limits and abort levels. MVF was designed to vibration test MPCV Orion and was used to perform the system level vibration test of the European Service Module Structural Test Article (E-STA) in 2016. MVF is comprised of an 18 ft diameter annulus table that is driven with sixteen hydraulic vertical actuator assemblies and four hydraulic horizontal actuator assemblies, which allow it to perform single axis vibration testing in the vertical axis and in each of the two orthogonal horizontal axes without the need for reconfiguring the test article. A head expander for the MVF Table has been designed and built that fills in the center opening providing a continuous flat mounting surface with a maximum diameter of 16.25feet that expands the vibration testing capabilities of MVF. The MVF Table with this head expander will be used during the SNC Dream Chaser spacecraft vibration test campaign. Therefore, a critical element in a test-verified model of the MVF will be a test correlated finite element model (FEM) of the head expander. To obtain this, engineers from the Structural Dynamics Lab (SDL) at NASA Glenn Research Center (GRC) in Cleveland, Ohio performed a modal pretest analysis, conducted a modal test in July 2019, and most recently correlated the head expander finite element model to the modal test data up to 300 Hz. From the initial test preparations to the final delivery of a correlated finite element model, all efforts mentioned were led by the same early-career engineers at NASA GRC. From the viewpoint of an early-career engineer, lessons learned about modal pretest analysis, modal testing, and finite element model correlation of the MVF Table expander head will be presented and discussed. This will include the importance of understanding the limitations of using uncorrelated finite element models in the modal pretest analysis and planning, the importance of orthogonality metrics in judging adequacy and accuracy of test mode shapes, and the importance of having the FEM match the as built hardware in the model correlation effort.

Emma L Pierson↗
NASA NTRSDate not supplied

Dynamic Characterization of NASA Armstrong Test Facility Mechanical Vibration Facility

In preparation for Sierra Nevada Corporation’s (SNC) Dream Chaser spacecraft vibration test campaign at NASA Armstrong Test Facility (ATF) in Sandusky, Ohio, a dynamic characterization of the Mechanical Vibration Facility (MVF) is currently ongoing. The Mechanical Vibration Facility is comprised of an 18 ft diameter annulus table that is driven with sixteen hydraulic vertical actuator assemblies and four hydraulic horizontal actuator assemblies. During a test campaign this allows for single axis vibration testing in the vertical axis and in each of the two orthogonal horizontal axes without the need for reconfiguring the test article. The dynamic characterization of the facility was defined to follow a building-block approach requiring three vibration test configurations: (1) MVF bare table (2) MVF table and head expander (3) MVF table, head expander, and a dummy test article. Following the completion of the facility dynamic characterization, a facility finite element model (FEM) will be test-verified allowing for more accurate pretest analysis used for determining response limits and abort levels. To date two of the three test configurations have been completed. Test results have been used to verify the facility FEM that includes both the 18 ft diameter annulus table and the aluminum head expander that fills in the center opening of the annulus to provide a continuous flat mounting surface. Both the MVF table and the head expander models were previously correlated using test results from free-free boundary condition modal tests so model updates to the facility FEM focused on the uncorrelated vertical actuator assemblies and horizontal actuator assemblies. The accuracy of the test-verified facility FEM will be further determined based on comparison of analytical and test results from the vibration test of the dummy test article. Efforts will also be made to determine fixed base modes of the test article attached to the flexible vibration table using fixed base correction techniques. This paper will discuss test and analytical results from the MVF dynamic characterization test sequence and corresponding model updating effort.

Emma L Pierson↗
NASA NTRS2014

Deducing Electronic Unit Internal Response During a Vibration Test Using a Lumped Parameter Modeling Approach

During random vibration testing of electronic boxes there is often a desire to know the dynamic response of certain internal printed wiring boards (PWBs) for the purpose of monitoring the response of sensitive hardware or for post-test forensic analysis in support of anomaly investigation. Due to restrictions on internally mounted accelerometers for most flight hardware there is usually no means to empirically observe the internal dynamics of the unit, so one must resort to crude and highly uncertain approximations. One common practice is to apply Miles Equation, which does not account for the coupled response of the board in the chassis, resulting in significant over- or under-prediction. This paper explores the application of simple multiple-degree-of-freedom lumped parameter modeling to predict the coupled random vibration response of the PWBs in their fundamental modes of vibration. A simple tool using this approach could be used during or following a random vibration test to interpret vibration test data from a single external chassis measurement to deduce internal board dynamics by means of a rapid correlation analysis. Such a tool might also be useful in early design stages as a supplemental analysis to a more detailed finite element analysis to quickly prototype and analyze the dynamics of various design iterations. After developing the theoretical basis, a lumped parameter modeling approach is applied to an electronic unit for which both external and internal test vibration response measurements are available for direct comparison. Reasonable correlation of the results demonstrates the potential viability of such an approach. Further development of the preliminary approach presented in this paper will involve correlation with detailed finite element models and additional relevant test data.

random vibration response↗
DOE OSTI2024

Nonequivalent Atomic Vibrations at Interfaces in a Polar Superlattice

In heterostructures made from polar materials, e.g., AlN–GaN–AlN, the nonequivalence of the two interfaces is long recognized as a critical aspect of their electronic properties; in that, they host different 2D carrier gases. Interfaces play an important role in the vibrational properties of materials, where interface states enhance thermal conductivity and can generate unique infrared-optical activity. The nonequivalence of the corresponding interface atomic vibrations, however, is not investigated so far due to a lack of experimental techniques with both high spatial and high spectral resolution. Herein, the nonequivalence of AlN–(Al 0.65 Ga 0.35 )N and (Al 0.65 Ga 0.35 )N–AlN interface vibrations is experimentally demonstrated using monochromated electron energy-loss spectroscopy in the scanning transmission electron microscope (STEM-EELS) and density-functional-theory (DFT) calculations are employed to gain insights in the physical origins of observations. It is demonstrated that STEM-EELS possesses sensitivity to the displacement vector of the vibrational modes as well as the frequency, which is as critical to understanding vibrations as polarization in optical spectroscopies. The combination enables direct mapping of the nonequivalent interface phonons between materials with different phonon polarizations. Furthermore, the results demonstrate the capacity to carefully assess the vibrational properties of complex heterostructures where interface states dominate the functional properties.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ultrafast spectroscopic studies of vibrational energy transfer in energetic materials

Shock-induced detonation is a key property of energetic materials (EM) that remains empirically understood. One proposed mechanism of shock-initiation in EM is “phonon up-pumping” to initiate chemical reactions, where excitation of lattice phonon modes rapidly transfers energy into intramolecular vibrations, ultimately resulting in the breaking of chemical bonds. We are developing novel ultrafast laser spectroscopy techniques to study vibrational energy transfer from phonon modes to intramolecular vibrations (phonon up-pumping), as well as competing energy transfer pathways from intramolecular vibrations to phonon modes (vibrational cooling). Through combinations of plasma- generated supercontinuum infrared, tunable near- and mid-infrared, and terahertz pulses in pump-probe spectroscopy, supplemented with ab inito simulations, we can explore the energy transfer processes on a sub-picosecond time scale to elucidate vibrational energy transfer pathways and lifetimes in EM. In this work, we highlight recent progress, including the spectral and temporal characteristics of the infrared and THz sources as well as preliminary results on select EM.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Wireless Sensor Modalities at a Nuclear Plant Site to Collect Vibration Data

One of the major contributors to the total operating costs of domestic nuclear fleet of reactors today is the operation and maintenance (O&M) costs. These include labor-intense preventive maintenance programs involving manually-performed inspection, calibration, testing, and maintenance of plant assets at periodic frequency and time-based replacement of assets at periodic frequency, irrespective of their conditions. This has resulted in a labor-centric business model to achieve high capacity factors. To build an optimal maintenance program, it’s time to transition from this labor-centric business model to a technology-centric business model. Fortunately, there are technologies (advanced sensor, data analytics, and risk assessment methodologies) that will support this transition. The technology-centric business model will result in significant plant life extension and reduction of time-based maintenance activities. This will drive down O&M costs as labor is a rising cost and technology is a declining cost. This approach will lay the foundation for real-time condition assessment of plant assets, allowing condition-based maintenance to enhance plant safety, reliability, and economics of operation. The goal of this project is to address challenges in the area of digital monitoring, i.e., the application of advanced sensor technologies (particularly wireless sensor technologies) and science-based data analytic capabilities to advance online monitoring and predictive maintenance in nuclear plants to improve plant performance (efficiency gain and economic competitiveness). To achieve the project goal, in partnership with Exelon Generating Company (Exelon), researchers from Idaho National Laboratory (INL) and Oak Ridge National Laboratory (ORNL) are performing research and development (R&D) to demonstrate application of wireless sensors using the distributed antenna system and advanced data analytics to achieve predictive maintenance. In the report, wireless vibration sensors, vibration data and its indicator are described. The wireless vibration sensors presented in this report support three types of wireless communication, namely, Wi-Fi, cellular, and 900 MHz. These wireless vibration sensors are considered by partner plant site for installation on plant asset to enable online vibration monitoring to replace periodic measurements. These vibration data along with other plant process data will be utilized to develop diagnostic and prognostic models.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS2002

Ab initio calculations of anharmonic vibrational spectroscopy for hydrogen fluoride (HF)n (n = 3, 4) and mixed hydrogen fluoride/water (HF)n(H2O)n (n = 1, 2, 4) clusters

Anharmonic vibrational frequencies and intensities are computed for hydrogen fluoride clusters (HF)n, with n = 3, 4 and mixed clusters of hydrogen fluoride with water (HF)n(H2O)n where n = 1, 2. For the (HF)4(H2O)4 complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Potential energy surfaces for these systems are obtained at the MP2/TZP level of electronic structure theory. Vibrational states are calculated from the potential surface points using the correlation-corrected vibrational self-consistent field method. The method accounts for the anharmonicities and couplings between all vibrational modes and provides fairly accurate anharmonic vibrational spectra that can be directly compared with experimental results without a need for empirical scaling. For (HF)n, good agreement is found with experimental data. This agreement shows that the Moller-Plesset (MP2) potential surfaces for these systems are reasonably reliable. The accuracy is best for the stiff intramolecular modes, which indicates the validity of MP2 in describing coupling between intramolecular and intermolecular degrees of freedom. For (HF)n(H2O)n experimental results are unavailable. The computed intramolecular frequencies show a strong dependence on cluster size. Intensity features are predicted for future experiments.

Water/chemistry↗
NASA NTRS2014

Signal Processing Methods for Removing the Effects of Whole Body Vibration upon Speech

Humans may be exposed to whole-body vibration in environments where clear speech communications are crucial, particularly during the launch phases of space flight and in high-performance aircraft. Prior research has shown that high levels of vibration cause a decrease in speech intelligibility. However, the effects of whole-body vibration upon speech are not well understood, and no attempt has been made to restore speech distorted by whole-body vibration. In this paper, a model for speech under whole-body vibration is proposed and a method to remove its effect is described. The method described reduces the perceptual effects of vibration, yields higher ASR accuracy scores, and may significantly improve intelligibility. Possible applications include incorporation within communication systems to improve radio-communication systems in environments such a spaceflight, aviation, or off-road vehicle operations.

human response to vibration↗
NASA NTRS2020

Vibration-based health characterization of multiple IMUs in UAV applications

Inertial measurement units (IMUs) are vital in UAV navigation for vehicle attitude and position estimation, especially in the frequently-occurring case of temporary loss of GPS capabilities. Degradation in these units could yield inaccurate position estimates, resulting in incorrect input for vehicle control systems. A wide variety of these units exist to meet the needs of UAV operators, general aviation, and military vehicles. In recent decades, lightweight and inexpensive MEMS sensors have grown in popularity with respect to UAVs. Studies into the failure modes of MEMS devices suggest that vibration is one of the leading causes of MEMS degradation. MEMS sensors are generally encased in their own hermetic packaging, as their small size and sensitivity cause them to be particularly vulnerable to air damping and particulate contamination when exposed. Exposure to excessive vibration can cause cracking in this packaging as well as damage to connecting electronics, with recorded results that cause sensors to act outside of their specifications, potentially providing unreliable input to controllers. A prior study from the Politecnico di Torino looked into the degradation of MEMS IMUs, specifically the AXIS-AIS402, for aerospace and vibrating environments. In the study, the authors found that after exposing MEMS IMUs to simulated vibrations from working conditions of aerospace applications, the sensors showed increased noise and increased bias instability. At NASA Ames, several widely-used MEMS IMUs were selected for a new IMU degradation study, comparing accelerometer performance before and after exposure to similar levels of vibration simulating aerospace conditions. The IMUs were selected from the Pixhawk autopilot systems, hobby sUAS, or prior experimental studies at NASA. Additionally, the industrial grade VectorNav-100 IMU was selected as a ground truth reference point to which the performance of the test sensors can be compared. In the study, each sensor is exposed to functional levels of UAV vibration as replicated on a single-frequency vibratory table in the NASA Ames SHARP Laboratory, and each accelerometer is characterized for bias, drift, and noise characteristics both before and after vibratory exposure. The focus of this study is to monitor the health of the IMU sensors and determine if sensor degradation can be detected from output error and frequency spectrum analysis, rather than from microscopic examination of the sensors. In this case, sensor degradation and faulty data can be more easily detectable by non-experts hoping to use these sensors as an important piece of an integrated package. In addition, specific sensor degradation modes potentially leading to in-flight hazards could be identified, such as accelerated levels of drift and altered temperature response. The overall goal of this work is to increase levels of safety for future users of these sensors and to provide a clear analysis of sensor limitations currently lacking in most sensor specification documentation.

IMUs↗
DOE OSTI2023

Theory predicts UV/vis-to-IR photonic down conversion mediated by excited state vibrational polaritons

This work proposes a photophysical phenomenon whereby ultraviolet/visible (UV/vis) excitation of a molecule involving a Franck-Condon (FC) active vibration yields infrared (IR) emission by strong coupling to an optical cavity. The resulting UV/vis-to-IR photonic down conversion process is mediated by vibrational polaritons in the electronic excited state potential. It is shown that the formation of excited state vibrational polaritons (ESVP) via UV/vis excitation only involve vibrational modes with both a non-zero FC activity and IR activity in the excited state. Density functional theory calculations are used to identify 1-Pyreneacetic acid as a molecule with this property and the dynamics of ESVP are modeled. Overall, this work introduces an avenue of polariton chemistry where excited state dynamics are influenced by the formation of vibrational polaritons. Along with this, the UV/vis-to-IR photonic down conversion is potentially useful in both sensing excited state vibrations and quantum transduction schemes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Emergent interface vibrational structure of oxide superlattices

As the length scales of materials decrease, the heterogeneities associated with interfaces become almost as important as the surrounding materials. This has led to extensive studies of emergent electronic and magnetic interface properties in superlattices. However, the interfacial vibrations that affect the phonon-mediated properties, such as thermal conductivity, are measured using macroscopic techniques that lack spatial resolution. Although it is accepted that intrinsic phonons change near boundaries, the physical mechanisms and length scales through which interfacial effects influence materials remain unclear. Here we demonstrate the localized vibrational response of interfaces in strontium titanate–calcium titanate superlattices by combining advanced scanning transmission electron microscopy imaging and spectroscopy, density functional theory calculations and ultrafast optical spectroscopy. Structurally diffuse interfaces that bridge the bounding materials are observed and this local structure creates phonon modes that determine the global response of the superlattice once the spacing of the interfaces approaches the phonon spatial extent. Our results provide direct visualization of the progression of the local atomic structure and interface vibrations as they come to determine the vibrational response of an entire superlattice. Direct observation of such local atomic and vibrational phenomena demonstrates that their spatial extent needs to be quantified to understand macroscopic behaviour. Tailoring interfaces, and knowing their local vibrational response, provides a means of pursuing designer solids with emergent infrared and thermal responses.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Decoupling excitons from high-frequency vibrations in organic molecules

The coupling of excitons in π-conjugated molecules to high-frequency vibrational modes, particularly carbon–carbon stretch modes (1,000–1,600 cm -1 ) has been thought to be unavoidable. These high-frequency modes accelerate non-radiative losses and limit the performance of light-emitting diodes, fluorescent biomarkers and photovoltaic devices. Here, by combining broadband impulsive vibrational spectroscopy, first-principles modelling and synthetic chemistry, we explore exciton–vibration coupling in a range of π-conjugated molecules. We uncover two design rules that decouple excitons from high-frequency vibrations. First, when the exciton wavefunction has a substantial charge-transfer character with spatially disjoint electron and hole densities, we find that high-frequency modes can be localized to either the donor or acceptor moiety, so that they do not significantly perturb the exciton energy or its spatial distribution. Second, it is possible to select materials such that the participating molecular orbitals have a symmetry-imposed non-bonding character and are, thus, decoupled from the high-frequency vibrational modes that modulate the π-bond order. We exemplify both these design rules by creating a series of spin radical systems that have very efficient near-infrared emission (680–800 nm) from charge-transfer excitons. We show that these systems have substantial coupling to vibrational modes only below 250 cm -1 , frequencies that are too low to allow fast non-radiative decay. This enables non-radiative decay rates to be suppressed by nearly two orders of magnitude in comparison to π-conjugated molecules with similar bandgaps. Our results show that losses due to coupling to high-frequency modes need not be a fundamental property of these systems.

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

Resonant two-photon photoelectron imaging and adiabatic detachment processes from bound vibrational levels of dipole-bound states

Anions cannot have Rydberg states, but anions with polar neutral cores can support highly diffuse dipole-bound states (DBSs) as a class of interesting electronically excited states below the electron detachment threshold. The binding energies of DBSs are extremely small, ranging from a few to few hundred wavenumbers and generally cannot support bound vibrational levels below the detachment threshold. Thus, vibrational excitations in the DBS are usually above the electron detachment threshold and they have been used to conduct resonant photoelectron spectroscopy, which is dominated by state-specific autodetachment. Here we report an investigation of a cryogenically-cooled complex anion, the enantiopure (R)-(–)-1-(9-anthryl)-2,2,2-trifluoroethanolate (R-TFAE–). The neutral R-TFAE radical is relatively complex and highly polar with a non-planar structure (C 1 symmetry). Photodetachment spectroscopy reveals a DBS 209 cm–1 below the detachment threshold of R-TFAE– and seven bound and eight above-threshold vibrational levels of the DBS. Resonant two-photon detachment (R2PD) via the bound vibrational levels of the DBS exhibits strictly adiabatic photodetachment behaviors by the second photon, in which the vibrational energies in the DBS are carried to the neutral final states, because of the parallel potential energy surfaces of the DBS and the corresponding neutral ground electronic state. Relaxation processes from the bound DBS levels to the ground and low-lying electronically excited states of R-TFAE– are also observed in the R2PD photoelectron spectra. Finally, the combination of photodetachment and resonant photoelectron spectroscopy yields frequencies for eight vibrational modes of the R-TFAE radical.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗