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At least 883 records · Page 49

The Computer Program LIAR for Beam Dynamics Calculations in Linear Accelerators

Linear accelerators are the central components of the proposed next generation of linear colliders. They need to provide acceleration of up to 750 GeV per beam while maintaining very small normalized emittances. Standard simulation programs, mainly developed for storage rings, do not meet the specific requirements for high energy linear accelerators. We present a new program LIAR ('LInear Accelerator Research code') that includes wakefield effects, a 6D coupled beam description, specific optimization algorithms and other advanced features. Its modular structure allows to use and to extend it easily for different purposes. The program is available for UNIX workstations and Windows PC's. It can be applied to a broad range of accelerators. We present examples of simulations for SLC and NLC.

43 PARTICLE ACCELERATORS↗

Developing Load Cell Monitoring on the Mock UF 6 Feed and Withdrawal System

A proof-of-concept load cell monitoring system has been developed for the Mock Feed and Withdrawal (F&W) System at Oak Ridge National Laboratory (ORNL). This system leverages industry-standard commercial off-the-shelf (COTS) hardware and software in a modular and scalable design. The Mock F&W System was designed to simulate operations at a uranium hexafluoride (UF 6 ) gas centrifuge enrichment plant F&W area. It provides a test bed for process-monitoring technologies. Water, used as a surrogate for UF 6 , is pumped from three feed tanks, through a process surge tank, and is then cut between two tails tanks and three product tanks. The weight of the each tank is continuously monitored using a load cell monitoring system. In addition to the F&W stations, large and small accountancy stations are monitored. The Mock F&W System allows ORNL to test and evaluate capabilities of industry-standard process monitoring hardware and software. A variety of commonly used weighing indicators are connected to the load cells to monitor the weight at each station. These weighing indicators are representative of the types likely found in operating facilities. A data center modeled after those currently used for international safeguards was installed to collect and manage the weight data. This data center provides a robust and flexible test bed for testing and developing software solutions. COTS software packages that leverage industry-standard communication protocols provide a data flow architecture that is modular, interoperable, and scalable. One software package provides communication drivers to collect the raw weight data from the weighing indicators. A data historian is used to store the raw data. Custom in-house algorithms have been developed using MATLAB to analyze the raw historical data and to automatically identify process information. This information includes the number of cycles completed and the mass of material transferred from stations to the process. The process information identified by the analysis is stored in a Microsoft SQL Server database. Visualization concepts have been developed that display the analyzed process information alongside visually compelling plots and animations of the raw data. The load cell monitoring system developed on the Mock F&W System was designed as a proof of concept that could be scaled to a field trial at an operating facility. This system, built with industry standard hardware and software, has allowed ORNL to develop capabilities that provide confidence in the ability to leverage existing operator load cell monitoring equipment with minimal impact on operations. The international safeguards community is evaluating the use of load cell monitoring as an additional safeguards measure; this system demonstrates a practical solution to collect, store, analyze, and visualize load cell weight data.

commercial off the shelf↗

Clover: Compiler directed lightweight soft error resilience

This paper presents Clover, a compiler directed soft error detection and recovery scheme for lightweight soft error resilience. The compiler carefully generates soft error tolerant code based on idem-potent processing without explicit checkpoint. During program execution, Clover relies on a small number of acoustic wave detectors deployed in the processor to identify soft errors by sensing the wave made by a particle strike. To cope with DUE (detected unrecoverable errors) caused by the sensing latency of error detection, Clover leverages a novel selective instruction duplication technique called tail-DMR (dual modular redundancy). Once a soft error is detected by either the sensor or the tail-DMR, Clover takes care of the error as in the case of exception handling. To recover from the error, Clover simply redirects program control to the beginning of the code region where the error is detected. Lastly, the experiment results demonstrate that the average runtime overhead is only 26%, which is a 75% reduction compared to that of the state-of-the-art soft error resilience technique.

97 MATHEMATICS AND COMPUTING↗

Compiler-Directed Soft Error Detection and Recovery to Avoid DUE and SDC via Tail-DMR

This article presents Clover, a compiler-directed soft error detection and recovery scheme for lightweight soft error resilience. The compiler carefully generates soft-error-tolerant code based on idempotent processing without explicit checkpoints. During program execution, Clover relies on a small number of acoustic wave detectors deployed in the processor to identify soft errors by sensing the wave made by a particle strike. To cope with DUEs (detected unrecoverable errors) caused by the sensing latency of error detection, Clover leverages a novel selective instruction duplication technique called tail-DMR (dual modular redundancy) that provides a region-level error containment. Once a soft error is detected by either the sensors or the tail-DMR, Clover takes care of the error as in the case of exception handling. To recover from the error, Clover simply redirects program control to the beginning of the code region where the error is detected. The experimental results demonstrate that the average runtime overhead is only 26%, which is a 75% reduction compared to that of the state-of-the-art soft error resilience technique. In addition, this article evaluates an alternative technique called tail-wait, comparing it to Clover. According to the evaluation with the different processor configurations and the various error detection latencies, Clover turns out to be a superior technique, achieving 1.06 to 3.49× speedup over the tail-wait.

Computer Science↗

Nonlinear quantum interferometric spectroscopy with entangled photon pairs

Here, we develop closed expressions for a time-resolved photon counting signal induced by an entangled photon pair in an interferometric spectroscopy setup. Superoperator expressions in Liouville-space are derived that can account for relaxation and dephasing induced by coupling to a bath. Interferometric setups mix matter and light variables non-trivially, which complicates their interpretation. We provide an intuitive modular framework for this setup that simplifies its description. Based on the separation between the detection stage and the light–matter interaction processes, we show that the pair entanglement time and the interferometric time-variables control the observed physics time scale. Only a few processes contribute in the limiting case of small entanglement time with respect to the sample response, and specific contributions can be singled out.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Advanced, Radiation Resistant, Optical-based Detector Technology for Future Experiments.

The primary objective of this project has been to advance the design of high-performance electromagnetic (EM) calorimeters for future particle physics experiments, to identify and measure the timing, position and energy of electrons, positrons and gamma rays, particularly in high-luminosity environments with intense radiation and pileup conditions. To meet such challenges, the proposed research has focused on the development of ultra-compact, radiation-hard calorimeter modules, to provide excellent timing, spatial, and energy resolution. The work aligns with the DOE’s Basic Research Needs (BRN) for High Energy Physics (HEP) Instrumentation and the research team contributes actively to the Coordinating Panel on Advanced Detectors (CPAD) RDC9 calorimetry collaboration in the USA and the European Committee on Future Accelerators (ECFA) DRD-CALO calorimetry collaboration at CERN, the European Laboratory for Particle Physics located in Geneva, Switzerland. The research builds on the RADiCAL (radiation-hard, ultra-compact) modular sampling calorimeter approach, developed by the research team, which employs dense and very bright optical materials such as LYSO:Ce scintillator plates that are interleaved with very dense tungsten plates to minimize detector size while optimizing performance. The modules are comparable in size to a human index finger, dimensionally 14 mm x 14 mm in cross section and 135 mm in length. And despite the small size, the structure is capable of providing excellent timing and energy resolution. This is facilitated through the use of specialized quartz capillaries filled with wavelength-shifting filaments, positioned at various depths along the length of a module, to collect and guide light signals to silicon photomultipliers (SiPMs) which detect and convert the optical signals to electronic signals for analysis. The primary goals of this project have been: (1) Achieve a timing resolution to σ t ≤ 30 ps for high-energy electrons and photons, important for their association with specific events produced in colliding-beam experiments and for the detection of decays-in-flight of long-lived particles. The project has achieved this goal in beam tests of a single RADiCAL module at CERN, during which a timing resolution of σ t = 27 ps was measured for electrons of energy E = 150 GeV. Based upon a mathematical fit to the data measured over a broad energy range from low energy to high energy, a resolution of σ t ≤ 18 ps has been estimated for electrons of very high (TeV) energy. From these measurements and with further expected technical improvements, the timing resolution should reach σ t ≤ 10 ps, important for searches for discovery physics in upcoming and future experiments. (2) Achieve an energy resolution of σ E / E ≤ 10% / $\sqrt{E}$. The project has yet to achieve this goal, but is close to it, having measured a value of σ E / E ≤ 15.9% / $\sqrt{E}$ using a modular array. Ultimately, the resolution goal is expected to be reached by adjustments to material thicknesses within the modules, which will improve the sampling fraction to measure more precisely the shower energy for lower energy particles. The versatility of the modular RADiCAL approach enables the testing of advanced materials, photosensors and electronics, developed in collaboration with CPAD RDC and ECFA DRD-CALO groups. The structure can distinguish electrons, positrons and gamma rays from hadrons and muons and beam-induced backgrounds, making it a valuable tool in a variety of detector environments, including future circular colliders (FCC-ee, FCC-hh) proposed for the European Laboratory for Particle Physics (CERN), the muon-collider proposed for Fermi National Accelerator Laboratory (Fermilab), and searches for new physics in beam-dump, fixed target and forward-physics experiments. And, while designed with particle physics applications in mind, the technologies developed in this project have the potential for application more broadly in particle and nuclear physics, materials science, and medical physics, underscoring the far-reaching potential of this line of instrumentation research and development.

47 OTHER INSTRUMENTATION↗

Entanglement wedge reconstruction using the Petz map

At the heart of recent progress in AdS/CFT is the question of subregion duality, or entanglement wedge reconstruction: which part(s) of the boundary CFT are dual to a given subregion of the bulk? This question can be answered by appealing to the quantum error correcting properties of holography, and it was recently shown that robust bulk (entanglement wedge) reconstruction can be achieved using a universal recovery channel known as the twirled Petz map. In short, one can use the twirled Petz map to recover bulk data from a subset of the boundary. However, this map involves an averaging procedure over bulk and boundary modular time, and hence it can be somewhat intractable to evaluate in practice. We show that a much simpler channel, the Petz map, is sufficient for entanglement wedge reconstruction for any code space of fixed finite dimension – no twirling is required. Moreover, the error in the reconstruction will always be non-perturbatively small. From a quantum information perspective, we prove a general theorem extending the use of the Petz map as a general-purpose recovery channel to subsystem and operator algebra quantum error correction.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Structural characterization of the principal mRNA-export factor Mex67–Mtr2 from Chaetomium thermophilum

The crystal structures of the individual domains of the Mex67–Mtr2 complex from C. thermophilum have been determined and their arrangement in solution has been studied by SAXS. Members of the Mex67–Mtr2/NXF–NXT1 family are the principal mediators of the nuclear export of mRNA. Mex67/NXF1 has a modular structure based on four domains (RRM, LRR, NTF2-like and UBA) that are thought to be present across species, although the level of sequence conservation between organisms, especially in lower eukaryotes, is low. Here, the crystal structures of these domains from the thermophilic fungus Chaetomium thermophilum are presented together with small-angle X-ray scattering (SAXS) and in vitro RNA-binding data that indicate that, not withstanding the limited sequence conservation between different NXF family members, the molecules retain similar structural and RNA-binding properties. Moreover, the resolution of crystal structures obtained with the C. thermophilum domains was often higher than that obtained previously and, when combined with solution and biochemical studies, provided insight into the structural organization, self-association and RNA-binding properties of Mex67–Mtr2 that facilitate mRNA nuclear export.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Applicability Evaluation of the In-can Vitrification to Fukushima Waste - 19016

The in-can vitrification process has been developed by the CEA for an internal application (alpha waste treatment) since 2005 and can be rated TRL 7. On these basis the DEM'n'MELT consortium which gathers Orano, CEA and ECM technologies is currently developing and qualifying a robust, simple and versatile in situ vitrification process dedicated to D and D waste. The DEM'n'MELT vitrification process is developed with a modular design, the main characteristics are presented hereafter: - Suitable for high or medium level waste. - Heated by a simple and robust resistance furnace. - Offering homogeneity to the melted mixture. - Suitable for solid or liquid wastes, including zeolites and sludge. - Flexible enough to accommodate uncertainties on waste composition. - Designed in order to produce a small amount of secondary waste. - Implementing proven technological solutions from French high level vitrification shops. - Requiring low investment and operation costs. Regarding this features, the in-can process has been deemed as an appropriate tool for the vitrification of the Fukushima water treatment secondary waste (mineral adsorbants, sludge). The evaluation of the In-can process for Fukushima waste is a project led by Orano, CEA and ANADEC. The main phases are: - Scenarios and glass formulation studies to optimize waste loading and matrix homogeneity. - Bench scale tests on several scenarios of blended waste. - Pilot scale test on one selected scenario (reference scenario). - Feasibility evaluation to Fukushima Daiichi Nuclear Power Station implementation. This paper presents the first results of this project with a highlighting on glass waste loading, glass properties, bench tests and pilot test results, process parameters, and material balance. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Hamilton: Flexible, Open Source $10 Wireless Sensor System for Energy Efficient Building Operation

Sensors for improving building performance are rapidly populating the market, driven in part by the drive to reduce greenhouse gas emissions resulting from energy production as well as improve the interior environment for healthy and more productive spaces. UC Berkeley has led wireless sensor development over the past 25 years (e.g., Telos mote), with the Hamilton (named after Alexander Hamilton on the US $10 bill) as the most recent. The Hamilton sensor was designed as a low-cost high-performance sensor that is modular and interoperable. The objective of the Hamilton project was to create, evaluate and establish the technological foundations for secure and easy to deploy building energy efficiency applications utilizing pervasive, low-cost wireless sensors integrated with traditional Building Management Systems (BMS), consumer-sector building components, and powerful data analytics. The project included iterative hardware design, incorporating a high-performance database (BTrDb, http://btrdb.io/), creating and iterating the development of secure data middleware (BOSSwave, WAVE/WAVEMQ), working with and pushing the development of an open-source tiny operating system RiotOS, and implementing and improving protocols such as Thread/OpenThread and TCP/IP. The hardware benefited from careful design to drive down the cost; the design included a System-on-a-Chip (SoC), chip antenna, single crystal and five passive components. Careful design of the operating system created a low-power design to enable a long life with small batteries. The hardware included several sensors: temperature, radiant temperature, relative humidity, magnetometer, accelerometer, and light, with an optional occupancy (Passive InfraRed) sensor. The project was the basis of several applications, both internal to the research team and other researchers and professionals at other institutions. Several applications used the sensor hardware as the basis for other complex devices. Other applications used the sensors to improve building performance through interoperating with the building Heating Ventilation and Air-Conditioning (HVAC) system, such as using occupancy and/or distributed temperature sensing to reduce HVAC zone energy while still providing thermal comfort and to reduce peak loads in small commercial buildings. We demonstrated cloud-based energy analytics, implemented a schedule and a Model Predictive Controller in a small commercial building to optimize HVAC energy, occupancy and electricity price. Initial integration of these technological innovations was performed through the creation of execution containers containing the WAVE agent and various driver, proxy, or building system function logic. The research added to the understanding of efficient sensor hardware, secure middleware, time-series data management (high performance database), efficient communication protocols, and interoperating with applications and building systems. The project showed the technical effectiveness and economic feasibility of creating a low-cost, modular, and easy-to-deploy sensor. Through conversations with multiple end users, the research team discovered that many customers wanted data management and services in addition to the sensors. HamiltonIOT developed packages of sensors, border router, and data services to provide a seamless “plug-and-play” sensor deployment. Some customers were willing to pay for higher quality sensors (such as light); some customers wanted a robust enclosure (waterproof).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

What is the entropy in entropic gravity?

We explore theories in which gravity arises as a consequence of entropy. We distinguish between two approaches to this idea: holographic gravity, in which Einstein’s equation arises from keeping entropy stationary in equilibrium under variations of the geometry and quantum state of a small region, and thermodynamic gravity, in which Einstein’s equation emerges as a local equation of state from constraints on the area of a dynamical light sheet in a fixed spacetime background. Examining holographic gravity, we argue that its underlying assumptions can be justified in part using recent results on the form of the modular energy in quantum field theory. For thermodynamic gravity, on the other hand, we find that it is difficult to formulate a self-consistent definition of the entropy, which represents an obstacle for this approach. Our investigation points the way forward in understanding the connections between gravity and entanglement.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Fabrication and testing of a 4-node micro-pocket fission detector array for the Kansas State University TRIGA Mk. II research nuclear reactor

Advancements in nuclear reactor core modeling and computational capability have encouraged further development of in-core neutron sensors. Micro-Pocket Fission Detectors (MPFDs) have been fabricated and tested previously, but successful testing of these prior detectors was limited to single-node operation with specialized designs. Described in this work is a modular, four-node MPFD array fabricated and tested at Kansas State University (KSU). The four sensor nodes were equally spaced to span the length of the fuel-region of the KSU TRIGA Mk. II research nuclear reactor core. The encapsulated array was filled with argon gas, serving as an ionization medium in the small cavities of the MPFDs. The unified design improved device ruggedness and simplified construction over previous designs. A 0.315-in. (8-mm) penetration in the upper grid plate of the KSU TRIGA Mk. II research nuclear reactor was used to deploy the array between fuel elements in the core. The MPFD array was coupled to an electronic support system which has been developed to support pulse-mode operation. Neutron-induced pulses were observed on all four sensor channels. Stable device operation was confirmed by testing under steady-state reactor conditions. Each of the four sensors in the array responded to changes in reactor power between 10 kWth and full power (750 kWth). Reactor power transients were observed in real-time including positive transients with periods of 5, 15, and 30 s. Manual reactor power oscillations were observed in real-time.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

ISOTHERMAL AIR-INGRESS VALIDATION EXPERIMENTS

Idaho National Laboratory has conducted airingress experiments as part of a campaign to validate computational fluid dynamics (CFD) calculations for very high-temperature gas-cooled reactor (VHTR) analysis. An isothermal test loop was designed to recreate exchange or stratified flow that occurs in the lower plenum of VHTR after a break in the primary loop allows helium to leak out and reactor building air to enter the reactor core. The experiment was designed to measure stratified flow in the inlet pipe connecting to the lower plenum of the General Atomics gas turbine–modular helium reactor (GT-MHR). Instead of helium and air, brine and sucrose were used as heavy fluids, and water was used as the lighter fluid to create, using scaling laws, the appropriate flow characteristics of the lower plenum immediately after depressurization. These results clearly indicate that stratified flow is established even for very small density differences. Corresponding CFD results were validated with the experimental data. A grid sensitivity study on CFD models was also performed using the Richardson extrapolation and the grid convergence index method for the numerical accuracy of CFD calculations. The calculated current speed showed very good agreement with the experimental data, indicating that current CFD methods are suitable for simulating density gradient stratified flow phenomena in an air-ingress accident.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Enabling Dynamic Probabilistic Risk Assessment of Physical Security Using EMRALD and MAAP

The optimization of physical security in nuclear power plants requires sophisticated methodologies that integrate operator actions and plant behavior through advanced simulation tools. To address this, Idaho National Laboratory [JL2.1]has developed the Modeling and Analysis for Safety and Security using the Dynamic EMRALD Framework (MASS-DEF) methodology, an approach that integrates force-on-force simulations, dynamic probabilistic risk assessment, and thermal-hydraulics modeling [JL3.1]to enhance security planning while reducing costs. We developed a tool that produces reduced order models using thermal hydraulic simulations from the Modular Accident Analysis Program (MAAP) [1]. These models can quickly evaluate reactor core behavior during attack simulations, and in so doing, address two barriers of traditional methods: (1) MAAP simulations are computationally intensive, and (2) attack scenarios must be run in a secure environment, which complicates analysis and validation. By precomputing scenario outcomes for a small number of modified parameters, the reduced order model significantly decreases the computational cost and enables offsite review of the results.

22 - GENERAL STUDIES OF NUCLEAR REACTORS↗

Project Plan: Salt in Situ Heater Test

This project plan gives a high-level description of the US Department of Energy Office of Nuclear Energy (DOE-NE) Spent Fuel and Waste Disposition (SFWD) campaign in situ borehole heater test project planned for the Waste Isolation Pilot Plant (WIPP) site, titled the Brine Availability Test in Salt (BATS). BATS is the first stage in a planned sequence of tests to bolster the technical basis for disposal of heat generating waste in salt. This plan provides an overview of the schedule and responsibilities of the parties involved. This project is a collaborative effort by Sandia, Los Alamos, and Lawrence Berkeley National Laboratories to execute a series of small-diameter borehole heater tests in salt for the DOE-NE SFWD campaign. Design of a heater test in salt at WIPP has evolved over several years. The experiment has begun in January 2020 and the first phase will continue for several months with the possibility for follow on testing. BATS comprises a suite of modular tests, which consist of a group of adjacent horizontal boreholes in the wall of drifts at WIPP. Each test is centered around a packer-isolated heated borehole (12.2 cm [4.81 diameter) containing equipment for water-vapor collection and borehole closure monitoring, surrounded by smaller-diameter (up to 5.3 cm [2.11 diameter) satellite observation boreholes. Observation boreholes contain grouted-in temperature sensors, electrical resistivity tomography (ERT) sensors, and fiber optics; packer-isolated tracer release and sampling intervals; and acoustic emission (AE) piezoelectric sensors. A larger-diameter (12.2 cm [4.81) satellite borehole includes sorel and salt cement plugs, as part of an engineered barrier sealing test. The first two tests, to be implemented in parallel, are heated (target borehole wall temperature of 120 °C) and unheated, with similar arrays of observation borehole monitoring changes. Follow-on tests will be designed using information gathered from the first two tests, and may be conducted at other borehole wall temperatures, use multiple observation boreholes, and may include different measurement types and test designs. This 2020 update of the original 2018 project plan satisfies DOE-NE Spent Fuel and Waste Science and Technology (SFWST) milestone M3SF-205N010303034, as part of the SNL "Salt Disposal R&D" work package.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Stacked, filtered multi-channel X-ray diode array

There are many types of X-ray diodes used for X-ray flux or spectroscopic measurements and for estimating the spectral shape of the VUV to soft X-ray spectrum. However, a need exists for a low-cost, robust X-ray diode to use for experiments in hostile environments on multiple platforms, and for experiments that utilize forces that may destroy the diode(s). Since the typical proposed use required a small size with a minimal single line-of-sight, a parallel array could not be used. So, a stacked, filtered multi-channel X-ray diode array was developed, called the MiniXRD. To achieve significant cost savings while maintaining robustness and ease of field setup, repair, and replacement, we designed the system to be modular. The filters were manufactured in-house and cover the range from 450 eV to 5000 eV. To achieve the line-of-sight accuracy needed, we developed mounts and laser alignment techniques. We modeled and tested elements of the diode design at NSTec Livermore Operations (NSTec / LO) to determine temporal response and dynamic range, leading to diode shape and circuitry changes to optimize impedance and charge storage. The authors fielded individual and stacked systems at several national facilities as ancillary "ride-along" diagnostics to test and improve the design usability. This paper presents the MiniXRD system performance, which supports consideration as a viable low-costalternative for multiple-channel low-energy X-ray measurements. This diode array is currently at Technical Readiness Level (TRL) 6.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Application of Microscale Devices for Megawatt Scale Concentrating Solar Power Plants

Concentrated solar power (CSP) plants have the potential to reduce the consumption of non-renewable resources and greenhouse gas emissions in electricity production. In CSP systems, a field of heliostats focuses solar radiation on a central receiver, which is ultimately transferred to thermal electrical power plant at high temperature. However, the maximum receiver surface fluxes are low (30–100 W cm−2) with high thermal losses, which has limited the market penetration of CSP systems. Recently, small (∼ 4 cm2), laminated micro-channel devices have shown potential to achieve concentrated surface fluxes over 100 W cm−2 using supercritical CO2 as the working fluid. The present study explores the feasibility of using these microscale devices as building blocks for a megawatt scale (250 MW thermal) open solar receiver. This allows for a modular design of the central receiver with non-standard shapes customized to the heliostat field. The results show that the microscale unit-cells have the potential to be scaled to megawatt applications while providing high heat flux and thermal efficiency. At the design incident flux and surface emissivity, a global receiver thermal efficiency of > 90% can be achieved.

14 SOLAR ENERGY↗

Vibrational coherence transfer illuminates dark modes in models of the FeFe hydrogenase active site

Within the conceptual framework of Redfield theory, the optical response function arises from the dynamical evolution of the system’s density operator, where nonunitary relaxation is encoded in the Redfield relaxation superoperator. In the conventional approach, the so-called secular approximation neglects terms that induce transitions between distinct coherences and among coherences and populations. The rationale is that these nonsecular terms are small in comparison to the far more dominant population relaxation and coherence dephasing contributions. Since two-dimensional infrared (2D-IR) spectroscopy has significant contributions arising from population relaxation and transfer pathways, it can be challenging to isolate signatures of the nonsecular relaxation. We report om this paper that in three diiron dithiolate hexacarbonyl complexes that serve as small-molecule models of the [FeFe] hydrogenase H-cluster subsite, a fortuitous vibrational energy structure enables direct and clear signatures of vibrational coherence transfer in alkane solution. This finding holds promise towards developing a molecularly detailed understanding of the mechanism of vibrational coherence transfer processes, thanks to the ease of synthesizing derivatives based on the chemical modularity of these well studied diiron compounds. In addition to the fundamental need to characterize coherence transfer in molecular spectroscopy, we find in this set of molecules a practical utility for the nonsecular dynamics: the ability to determine the frequency of an IR-inactive mode. A coherence generated during the waiting time of the 2D-IR measurement transfers to a coherence involving the single dark CO stretching mode, which modulates some peak amplitudes in the 2D spectrum, revealing its transient excitation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗