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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 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Breaking the Window of Detection: Using Multi-Scale Solute Tracer Studies to Assess Mass Recovery at the Detection Limit

Stream solute tracers are commonly injected to assess transport and transformation in study reaches, but results are biased toward the shortest and fastest storage locations. While this bias has been understood for decades, the impact of an experimental constraint on our understanding has yet to be considered. Here, we ask how different our understanding of reach- and segment-scale transport would be if our empirical limits were extended. We demonstrate a novel approach to manipulate experimental conditions and observe mass that is stored at timescales beyond the traditional reach-scale window of detection. We are able to explain the fate of an average of 26% of solute tracer mass that would have been considered as “lost” in a traditional study design across our 14 replicates, extending our detection limits to characterize flowpaths that would have been previously unmeasured. We demonstrate how this formerly lost mass leads to predicting lower magnitudes of gross gains and losses in individual reaches, and ultimately show that the network turnover we infer from solute tracers represents an upper limit on actual, expected behavior. Finally, we review the evolution of tracer studies and their interpretation including this approach and provide a proposed future direction to extend empirical studies to not-before-seen timescales.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Real-Time Fault Tracking and Ground Motion Prediction for Large Earthquakes With HR-GNSS and Deep Learning

Earthquake early warning (EEW) systems aim to forecast the shaking intensity rapidly after an earthquake occurs and send warnings to affected areas before the onset of strong shaking. The system relies on rapid and accurate estimation of earthquake source parameters. However, it is known that source estimation for large ruptures in real-time is challenging, and it often leads to magnitude underestimation. In a previous study, we showed that machine learning, HR-GNSS, and realistic rupture synthetics can be used to reliably predict earthquake magnitude. This model, called Machine-Learning Assessed Rapid Geodetic Earthquake model (M-LARGE), can rapidly forecast large earthquake magnitudes with an accuracy of 99%. Here, we expand M-LARGE to predict centroid location and fault size, enabling the construction of the fault rupture extent for forecasting shaking intensity using existing ground motion models. We test our model in the Chilean Subduction Zone with thousands of simulated and five real large earthquakes. The result achieves an average warning time of 40.5 s for shaking intensity MMI4+, surpassing the 34 s obtained by a similar GNSS EEW model. Our approach addresses a critical gap in existing EEW systems for large earthquakes by demonstrating real-time fault tracking feasibility without saturation issues. This capability leads to timely and accurate ground motion forecasts and can support other methods, enhancing the overall effectiveness of EEW systems. Additionally, the ability to predict source parameters for real Chilean earthquakes implies that synthetic data, governed by our understanding of earthquake scaling, is consistent with the actual rupture processes.

58 GEOSCIENCES↗
DOE OSTI2024

A Stereo Camera Simulator for Large-Eddy Simulations of Continental Shallow Cumulus Clouds Based on Three-Dimensional Path-Tracing

The complex spatial and temporal structure of cumulus clouds complicates their representation in weather and climate models. Classic meteorological instrumentation struggles to fully capture these features. Networks of multiple high-resolution hemispheric cameras are increasingly used to fill this data gap, and provide information on this missing multi-dimensional spatial information. In this study, a path-tracing algorithm is used to generate virtual camera images of resolved clouds in large-eddy simulations (LES). These images are then used as a camera network simulator, allowing reconstructions of three-dimensional cloud edges from the model output. Because the actual LES cloud field is fully known, the combined path-tracing and reconstruction method can be statistically analyzed. The method is applied to LES realizations of summertime shallow cumulus at the Jülich Observatory for Cloud Evolution (JOYCE), Germany, which also routinely operates a camera network. We find that the path-tracing method allows accurate reconstruction of up to 70% of the visible cloud edges. Additional sensitivity tests show that the method is robust for changes in its hyperparameters. The sensitivity to cloud optical thickness is also investigated, finding a cloud boundary placement error of approximately 182 m. This error can be considered typical for cloud boundary reconstruction using real stereo camera imagery. The results provide proof of principle for future use of the method for evaluating LES clouds against camera network imagery, and for further optimizing the configuration of such camera networks.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Projecting Large Fires in the Western US With an Interpretable and Accurate Hybrid Machine Learning Method

More frequent and widespread large fires are occurring in the western United States (US), yet reliable methods for predicting these fires, particularly with extended lead times and a high spatial resolution, remain challenging. In this study, we proposed an interpretable and accurate hybrid machine learning (ML) model, that explicitly represented the controls of fuel flammability, fuel availability, and human suppression effects on fires. The model demonstrated notable accuracy with a F 1 -score of 0.846 ± 0.012, surpassing process-driven fire danger indices and four commonly used ML models by up to 40% and 9%, respectively. More importantly, the ML model showed remarkably higher interpretability relative to other ML models. Specifically, by demystifying the “black box” of each ML model using the explainable AI techniques, we identified substantial structural differences across ML fire models, even among those with similar accuracy. The relationships between fires and their drivers, identified by our model, were aligned closer with established fire physical principles. The ML structural discrepancy led to diverse fire predictions and our model predictions exhibited greater consistency with actual fire occurrence. With the highly interpretable and accurate model, we revealed the strong compound effects from multiple climate variables related to evaporative demand, energy release component, temperature, and wind speed, on the dynamics of large fires and megafires in the western US. Our findings highlight the importance of assessing the structural integrity of models in addition to their accuracy. They also underscore the critical need to address the rise in compound climate extremes linked to large wildfires.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Development of an ERT‐Based Framework for Bentonite Buffers Monitoring From Laboratory Tests: 2. Quantitative Moisture Dynamics Estimation Model

Abstract The long‐term containment of high‐level radioactive waste in geological disposal repositories relies on Engineered Barrier Systems (EBS), with bentonite clay emerging as a candidate material due to its unique properties. Understanding moisture dynamics within bentonite buffers is crucial for EBS performance, as it directly influences the material's swelling capacity, thermal and hydraulic conductivity, mechanical properties, and long‐term evolution under complex thermal‐hydrological‐mechanical (THM) processes. This study develops an advanced Electrical Resistivity Tomography (ERT)‐based framework to quantitatively monitor moisture dynamics under THM conditions. Our framework extends the Waxman‐Smits model to incorporate the coupled effects of temperature, water content, fluid chemistry, and mechanical changes on bentonite's electrical properties. Utilizing HotBENT‐Lab data from our companion paper, which includes electrical conductivity, CT density, and thermocouple measurements, this study offers a novel methodological framework bridging different scales of the model. Our results show that the extended model can estimate water content from ERT data, capturing spatial and temporal variations in moisture distribution within bentonite columns. However, the model tends to overestimate water content compared to CT density‐derived measurements. We address this discrepancy by incorporating a simplified swelling effect model, which improves agreement between ERT and CT density‐based water content estimates. We also discuss model limitations, including simplified treatment of swelling and micropore effects, and propose a conceptual framework for transitioning from laboratory to field applications, addressing challenges such as parameter scalability, field validation methods, and integration of diverse data sources. This ERT‐based framework can potentially advance real‐world moisture monitoring of bentonite‐based EBS in nuclear waste repositories. Plain Language Summary Safely containing high‐level radioactive waste depends on barriers made from materials like bentonite clay, which is effective because it swells and seals in the waste. To ensure these barriers work well over time, it's important to understand how moisture moves through the clay. Our study developed a new method using ERT to monitor moisture levels in bentonite under conditions that mimic those in actual storage sites, including changes in temperature, water content, and mechanical stress. This study improved an existing model to better account for how these factors affect the clay, allowing us to create more accurate moisture maps. Initially, the proposed model overestimated the amount of water in the clay, but its accuracy was improved by factoring in how the clay swells when wet. This study also identified some limitations of the model and suggested ways to adapt it for use in real‐world waste storage sites. This new approach could lead to better monitoring and safety checks for nuclear waste storage systems, helping to ensure long‐term containment. Key Points This work develops an ERT‐based framework extending the Waxman‐Smits model to monitor bentonite moisture dynamics during coupled THM processes The extended model accurately estimates water content from Electrical Resistivity Tomography data, incorporating swelling effects to improve precision This work proposes a conceptual framework for transitioning from laboratory to field applications, advancing EBS monitoring in nuclear waste repositories

Chen, Hang↗
DOE OSTI2025

Space‐Time Causal Discovery in Earth System Science: A Local Stencil Learning Approach

Causal discovery tools enable scientists to infer meaningful relationships from observational data, spurring advances in fields as diverse as biology, economics, and climate science. Despite these successes, the application of causal discovery to space-time systems remains immensely challenging due to the high-dimensional nature of the data. For example, in climate sciences, modern observational temperature records over the past few decades regularly measure thousands of locations around the globe. To address these challenges, we introduce Causal Space-Time Stencil Learning (CaStLe), a novel meta-algorithm for discovering causal structures in complex space-time systems. CaStLe leverages regularities in local space-time dependencies to learn governing global dynamics. This local perspective eliminates spurious confounding and drastically reduces sample complexity, making space-time causal discovery practical and effective. For causal discovery, CaStLe flexibly accepts any appropriately adapted time series causal discovery algorithm to recover local causal structures. These advances enable causal discovery of geophysical phenomena that were previously unapproachable, including non-periodic, transient phenomena such as volcanic eruption plumes. Regularities in local space-time dependencies are transformed into informative spatial replicates, which actually improve CaStLe's performance when applied to ever-larger spatial grids. We successfully apply CaStLe to discover the atmospheric dynamics governing the climate response to the 1991 Mount Pinatubo volcanic eruption. We provide validation experiments to demonstrate the effectiveness of CaStLe over existing causal-discovery frameworks on a range of geophysics-inspired benchmarks while identifying the method's limitations and domains where its assumptions may not hold.

Nichol, J. Jake [Univ. of New Mexico, Albuquerque,↗
DOE OSTI2026

The Amazon River‐Breeze Circulation Limits Detection of Aerosol‐Cloud Interactions in Warm Clouds

Increased aerosol concentrations can brighten low-level clouds and extend their lifetimes, but aerosol–cloud interactions (ACI) remain highly uncertain and difficult to quantify. We show that part of this uncertainty is caused by topographical influences on clouds, that is, those arising from land–water contrasts. This is demonstrated using satellite retrievals in regions with extensive river networks, such as the Amazon Basin. 15 years of MODerate resolution Imaging Spectroradiometer (MODIS) satellite data show cloud formation over the Amazon River basin is suppressed by 26% with warm low clouds above the river exhibiting a 22% smaller droplet effective radius and 18% higher droplet concentration ($N_d$) compared to adjacent land clouds. Thus, clouds above the river may appear polluted but are actually influenced by river-breeze circulations driven by the thermal contrast between the river and the surrounding land. These responses are robust in both wet and dry seasons, and tests using an improved MODIS retrieval product show cloud differences are unlikely due to retrieval artifacts. In situ measurements from the Green Ocean Amazon Experiment (GoAmazon) confirm that $N_d$ is elevated above rivers and are also higher when carbon monoxide concentrations are elevated near the large city of Manaus. Lagrangian airmass tracking over Manaus shows that regional-scale river-breeze circulations impact $N_d$ as much as the urban aerosol plume, complicating ACI attribution and highlighting the need to isolate land-surface effects to assess ACI in continental regions.

Aerosol-Cloud Interactions↗
DOE OSTI2026

Reservoir Drought Resilience Under Future Warming Scenarios: Regional Disparities Across Heavily Regulated US Basins

Droughts across the U.S. have imposed substantial challenges to the management of water resources. Reservoir drought, one type of hydrological drought, is characterized by abnormally low reservoir storage levels, reflecting combined impacts of natural water shortages and water management practices. We investigate how reservoir drought signatures, particularly onset, severity, duration, recovery and frequency, may shift under rising temperatures, and how these shifts vary by reservoir typology and degree of regulation. By coupling atmosphere-land-river models with reservoir operations at ~12-km resolution, we simulated reservoir storage and characterized reservoir droughts across five heavily regulated U.S. basins. Our findings reveal significant regional and functional disparities in reservoir drought resilience under the scenario of rising temperatures. Reservoirs in the Texas-Gulf region are projected to become more resilient, while systems in the Upper Colorado and South Atlantic-Gulf regions face increased risk due to prolonged drought durations and slower recovery. With respect to primary function, reservoirs used for irrigation and hydropower, particularly those with smaller storage capacity and lower degrees of regulation, are most susceptible to future drought stress. These results are valuable in understanding water availability in highly regulated environments, and the influence of hydrometeorological conditions on storage dynamics. Overall, this study provides the first of its kind benchmark for reservoir droughts at a continental scale to support evolving multi-sectoral drought mitigation efforts. Future research is needed to link reservoir drought conditions to actual supply shortages across competing water uses, while leveraging existing adaptive management strategies and coordinated reservoir operations.

reservoir↗
DOE OSTI2026

The Value of Forecasters‐in‐the‐Loop in Real‐Time Flood Forecasting in the Age of Machine Learning

Machine learning (ML) applications in hydrological forecasting are increasingly prevalent and show great potential. However, many previous studies have only evaluated performance through reanalysis or retrospective simulations compared to simplified baselines. This study provides the first assessment of ML performance against actual operational forecasting systems operated by the California Nevada River Forecast Center (CNRFC), which combines the Community Hydrologic Prediction System (CHPS) with forecasters-in-the-loop. Results demonstrate that forecasters-in-the-loop systems consistently outperform ML models in both general forecasts and flood alerting across lead times up to 96 hr, even when ML models use observed forcings, while CNRFC operational process relies on biased weather forecasts. Our analysis reveals that forecaster expertise maintains forecast reliability despite inaccurate precipitation inputs, with human-guided systems showing superior performance degradation characteristics at extended lead times. These findings highlight the irreplaceable value of human expertise in operational forecasting and caution against overstating current ML capabilities in real-world applications.

Tran, Vinh Ngoc [Univ. of Michigan, Ann Arbor, MI ↗
DOE OSTI2026

Constraining the Aerosol Effects on Deep Convective Clouds by Considering the Coupling Between Clouds and the Planetary Boundary Layer

Several mechanisms have been proposed for the aerosol invigoration effect. Although their principles are well established, their actual magnitudes and roles in cloud development remain uncertain and debatable. This uncertainty partly stems from observational-based studies, in which it has been challenging to separate the co-variability between aerosols and meteorology. Addressing this problem requires large data samples. To this end, this study employs the Atmospheric Radiation Measurement data set expanding to 16 years (some up to 17 years, compared to 10 years in previous work) in the U.S. Southern Great Plains. It also conducts a more careful and rigorous analysis to isolate the influences of convective available potential energy (CAPE) and synoptic patterns to address a previously raised concern. We incorporated a new key process affecting aerosol-cloud interaction: cloud-surface coupling. The state/degree of the coupling relationship turns out to play an important role in the invigoration effect. Our analysis reinforces earlier findings of a robust positive relationship between cloud thickness and aerosol loading across CAPE percentiles—but only under cloud-surface coupled conditions. The increase in cloud thickness with aerosol loading is most pronounced in coupled clouds with high CAPE and bases below 1 km. Coupled clouds with bases below 1 km thicken between 1 and 4 km, depending on the CAPE percentile. Decoupled clouds show no such systematic changes. Synoptic patterns also lead to different strengths of the invigoration effect. Clean and polluted air masses are predominantly associated with northerly and southerly winds, respectively, with a stronger invigoration effect in cleaner air masses.

Geosciences↗
DOE OSTI2025

Baseflow Identification via Explainable AI With Kolmogorov‐Arnold Networks

Abstract Hydrological models often involve constitutive laws that may not be optimal in every application. We propose to replace such laws with the Kolmogorov‐Arnold networks (KANs), a class of neural networks designed to identify symbolic expressions. We demonstrate KAN's potential on the problem of baseflow identification, a notoriously challenging task plagued by significant uncertainty. KAN‐derived functional dependencies of the baseflow components on the aridity index outperform their original counterparts; they demonstrate that water availability, rather than potential evapotranspiration, drives baseflow by constraining actual evapotranspiration under arid conditions. On a test set, they increase the Nash‐Sutcliffe efficiency (NSE) by 65%, decrease the root mean squared error by 29%, and increase the Kling‐Gupta efficiency by 34%. This superior performance is achieved while reducing the number of fitting parameters from three to two. Next, we use data from 378 catchments across the continental United States to refine the water‐balance equation at the mean‐annual scale. The KAN‐derived equations based on the refined water balance outperform both the current aridity index model, with up to a 105% increase in NSE, and the KAN‐derived equations based on the original water balance. While the performance of our model and tree‐based machine learning methods is similar, KANs offer the advantage of simplicity and transparency and require no specific software or computational tools. This case study focuses on the aridity index formulation, but the approach is flexible and transferable to other hydrological processes. Plain Language Summary Equations used in hydrologic model are often suboptimal, resulting in reduced prediction accuracy and efficiency. We implemented Kolmogorov‐Arnold networks (KAN), a machine learning algorithm for deriving symbolic formulations, to estimate groundwater recharge and showed that it outperforms an existing state‐of‐the‐art semi‐empirical formulation. In hydrology, Nash‐Sutcliffe efficiency (NSE), root mean squared error (RMSE), and Kling‐Gupta efficiency (KGE) are commonly used to evaluate model performance. Higher NSE and KGE values indicate better performance, while lower RMSE values are preferable. Our results show that NSE increased by 71%, RMSE decreased by 32%, and KGE improved by 25%. In addition, KAN identifies an optimal functional form and can be used to derive new analytical formulas using the prior knowledge. The KAN‐inspired equation outperformed the original formulation and reduced the fitting parameters. Furthermore, we refined the water‐balance equation at the mean‐annual scale and showed that, based on the new water‐balance equation, KAN can derive new formulations that are superior to the original aridity index formulations (up to 105% increase in NSE) and KAN‐derived equations based on the original water balance. These findings highlight the significant potential of KAN to advance the scientific understanding of a wide range of hydrologic processes. Key Points Kolmogorov‐Arnold networks (KANs) enhance interpretability of machine‐learned hydrological models KAN‐derived symbolic formulations outperform state‐of‐the‐art semi‐empirical aridity indices KAN‐identified functional form yields an analytical index with fewer fitting parameters and improved performance

baseflow↗
DOE OSTI2026

Inverse Mapping of the Collision Kernel and Wall Flux Scaling in a Tall Convection‐Cloud Chamber Using Local Sensors and Knowledge‐Informed Deep Learning

Droplet collision–coalescence is a crucial process in cloud physics, but accurately representing this process under different dynamical conditions remains challenging. A proposed future convective‐cloud chamber aims to investigate this key process, but the method for observing it remains unclear, even though it is theoretically established that collision‐coalescence will occur. This study serves as a proof‐of‐concept demonstration of how knowledge‐informed deep learning, combined with measurement data from local sensors in the chamber, can be used to estimate the collision kernels, which determine how the droplet size distribution evolves during collision‐coalescence. In addition to estimating the collision kernel, we also address wall fluxes, another uncertain but important process that acts as a source of heat and moisture in the chamber. Ensemble runs of large‐eddy simulations are conducted by scaling the wall fluxes and the collision kernel, while the measured flow and cloud properties are used as inputs for a neural network. Results indicate that this approach successfully maps the scaling of wall fluxes and the collision kernel with biases of approximately 1% or less relative to the range of the target data. This proof‐of‐concept lays the groundwork for future applications; when the real measurements are available, real sensor data combined with the trained model presented in this work will enable estimation of the actual wall fluxes and collision kernel.

cloud chamber↗
DOE OSTI2021

Climate policy models need to get real about people — here’s how

Here, to predict how society and political systems might actually respond to warming, upgrade integrated assessment models. Political support for decarbonizing the global economy is at an all-time high. The good news is that about two-thirds of carbon emissions come from countries that have committed to reach ‘net zero’ by mid-century — they aim to cut their greenhouse-gas outputs and capture as much as they emit. The bad news? The computer models that analysts use to assess routes to achieve such goals are missing a crucial factor: politics.

Peng, Wei↗
DOE OSTI2020

Reaction mechanism and kinetics for CO 2 reduction on nickel single atom catalysts from quantum mechanics

Experiments have shown that graphene-supported Ni-single atom catalysts (Ni-SACs) provide a promising strategy for the electrochemical reduction of CO 2 to CO, but the nature of the Ni sites (Ni-N 2 C 2 , Ni-N 3 C 1 , Ni-N 4 ) in Ni-SACs has not been determined experimentally. Here, we apply the recently developed grand canonical potential kinetics (GCP-K) formulation of quantum mechanics to predict the kinetics as a function of applied potential (U) to determine faradic efficiency, turn over frequency, and Tafel slope for CO and H 2 production for all three sites. We predict an onset potential (at 10 mA cm –2 ) U onset = –0.84 V (vs. RHE) for Ni-N 2 C 2 site and U onset = –0.92 V for Ni-N 3 C 1 site in agreement with experiments, and U onset = –1.03 V for Ni-N 4 . We predict that the highest current is for Ni-N 4 , leading to 700 mA cm –2 at U = –1.12 V. To help determine the actual sites in the experiments, we predict the XPS binding energy shift and CO vibrational frequency for each site.

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

Distinct magneto-Raman signatures of spin-flip phase transitions in CrI 3

The discovery of 2-dimensional (2D) materials, such as CrI 3 , that retain magnetic ordering at monolayer thickness has resulted in a surge of both pure and applied research in 2D magnetism. Here, we report a magneto-Raman spectroscopy study on multilayered CrI 3 , focusing on two additional features in the spectra that appear below the magnetic ordering temperature and were previously assigned to high frequency magnons. Instead, we conclude these modes are actually zone-folded phonons. We observe a striking evolution of the Raman spectra with increasing magnetic field applied perpendicular to the atomic layers in which clear, sudden changes in intensities of the modes are attributed to the interlayer ordering changing from antiferromagnetic to ferromagnetic at a critical magnetic field. Our work highlights the sensitivity of the Raman modes to weak interlayer spin ordering in CrI 3 .

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

99 TcO 4 - removal from legacy defense nuclear waste by an alkaline-stable 2D cationic metal organic framework

Removal of 99 TcO 4 - from legacy defense nuclear tank waste at Savannah River Site is highly desirable for the purpose of nuclear safety and environmental protection, but currently not achievable given the extreme conditions including high alkalinity, high ionic strength, and strong radiation field. Herein, we present a potential solution to this long-term issue by developing a two-dimensional cationic metal organic framework SCU-103, showing ultrahigh stability in alkaline aqueous media and great resistance to both β and γ radiation. More importantly, it is very effective for 99 TcO 4 - separation from aqueous media as demonstrated by fast exchange kinetics, high sorption capacity, and superior selectivity, leading to the successful removal of 99 TcO 4 - from actual Savannah River Site high level tank waste for the first time, to the best of our knowledge. In addition, the uptake mechanism is comprehensively elucidated by molecular dynamics simulation and density functional theory calculation, showing a unique chemical recognition of anions with low charge density.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2020

In-plane uniaxial pressure-induced out-of-plane antiferromagnetic moment and critical fluctuations in BaFe 2 As 2

A small in-plane external uniaxial pressure has been widely used as an effective method to acquire single domain iron pnictide BaFe 2 As 2 , which exhibits twin-domains without uniaxial strain below the tetragonal-to-orthorhombic structural (nematic) transition temperature T s . Although it is generally assumed that such a pressure will not affect the intrinsic electronic/magnetic properties of the system, it is known to enhance the antiferromagnetic (AF) ordering temperature T N ( < T s ) and create in-plane resistivity anisotropy above T s . Here we use neutron polarization analysis to show that such a strain on BaFe 2 As 2 also induces a static or quasi-static out-of-plane ( c -axis) AF order and its associated critical spin fluctuations near T N / T s . Therefore, uniaxial pressure necessary to detwin single crystals of BaFe 2 As 2 actually rotates the easy axis of the collinear AF order near T N / T s , and such effects due to spin-orbit coupling must be taken into account to unveil the intrinsic electronic/magnetic properties of the system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

The role of mixed vibronic Q y -Q x states in green light absorption of light-harvesting complex II

The importance of green light for driving natural photosynthesis has long been underappreciated, however, under the presence of strong illumination, green light actually drives photosynthesis more efficiently than red light. This green light is absorbed by mixed vibronic Q y -Q x states, arising from chlorophyll (Chl)-Chl interactions, although almost nothing is known about these states. Here, we employ polarization-dependent two-dimensional electronic-vibrational spectroscopy to study the origin and dynamics of the mixed vibronic Q y -Q x states of light-harvesting complex II. We show the states in this region dominantly arise from Chl b and demonstrate how it is possible to distinguish between the degree of vibronic Q y versus Q x character. We find that the dynamics for states of predominately Chl b Q y versus Chl b Q x character are markedly different, as excitation persists for significantly longer in the Q x states and there is an oscillatory component to the Q x dynamics, which will be discussed. Our findings demonstrate the central role of electronic-nuclear mixing in efficient light-harvesting and the different functionalities of Chl a and Chl b .

59 BASIC BIOLOGICAL SCIENCES↗