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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Using Data Science Tools to Reveal and Understand Subtle Relationships of Inhibitor Structure in Frontal Ring-Opening Metathesis Polymerization

The rate of frontal ring-opening metathesis polymerization (FROMP) using the Grubbs generation II catalyst is impacted by both the concentration and choice of monomers and inhibitors, usually organophosphorus derivatives. Herein we report a data-science-driven workflow to evaluate how these factors impact both the rate of FROMP and how long the formulation of the mixture is stable (pot life). Using this workflow, we built a classification model using a single-node decision tree to determine how a simple phosphine structural descriptor (V bur-near ) can bin long versus short pot life. Additionally, we applied a nonlinear kernel ridge regression model to predict how the inhibitor and selection/concentration of comonomers impact the FROMP rate. Furthermore, the analysis provides selection criteria for material network structures that span from highly cross-linked thermosets to non-cross-linked thermoplastics as well as degradable and nondegradable materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Demonstration of a code coupling framework for modeling beam-collimator impacts in the advanced photon source

The high-brightness beams being produced in current and future accelerators present new machine protection concerns with the potential for high-energy-density (HED) conditions ( >100 J/mm 3 ) in beam-intercepting components. Simulating HED conditions in accelerators requires utilizing a suite of physics codes for particle dynamics, particle-matter interactions, and hydrodynamics. This paper describes a method of coupling the codes elegant, fluka, and flash to simulate the effects of a rapid beam loss in the advanced photon source storage ring and the resulting interaction of the beam and collimators. This paper expands previous work [J. Dooling et al., Collimator irradiation studies at the advanced photon source, in Proceedings of the IBIC-2023 (2023), pp. 245–249] by introducing a definition of the evolving geometry of the collimator surface as well as providing methods for simulating the absorption of synchrotron radiation and tracking shower particles produced during beam strikes. We demonstrate this framework by simulating machine conditions of the APS ring before and after its recent upgrade. Simulation results are compared with observed damage to collimators and test samples taken from the APS ring.

Accelerator/storage ring control systems↗
DOE OSTI2022

Meso-Scale Electrodynamic Coupling of the Earth Magnetosphere-Ionosphere System

Within the fully integrated magnetosphere-ionosphere system, many electrodynamic processes interact with each other. We review recent advances in understanding three major meso-scale coupling processes within the system: the transient field-aligned currents (FACs), mid-latitude plasma convection, and auroral particle precipitation. (1) Transient FACs arise due to disturbances from either dayside or nightside magnetosphere. As the interplanetary shocks suddenly compress the dayside magnetosphere, short-lived FACs are induced at high latitudes with their polarity successively changing. Magnetotail dynamics, such as substorm injections, can also disturb the current structures, leading to the formation of substorm current wedges and ring current disruption. (2) The mid-latitude plasma convection is closely associated with electric fields in the system. Recent studies have unraveled some important features and mechanisms of subauroral fast flows. (3) Charged particles, while drifting around the Earth, often experience precipitating loss down to the upper atmosphere, enhancing the auroral conductivity. Recent studies have been devoted to developing more self-consistent geospace circulation models by including a better representation of the auroral conductance. It is expected that including these new advances in geospace circulation models could promisingly strengthen their forecasting capability in space weather applications. The remaining challenges especially in the global modeling of the circulation system are also discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Splitting the Ring: Impact of Ortho and Meta Pi Conjugation Pathways through Disjointed [8]Cycloparaphenylene Electronic Materials

In this report, we describe the synthesis and electronic properties of small-molecule and polymeric [8]cycloparaphenylenes ([8]CPPs) with disjointed pi conjugated substituents. Arylene-ethynylene linkers were installed on opposite sides of the [8]CPP nanohoop as separated by three phenyl units on either side such that the monomer systems have syn (C2 symmetry) and anti (C1 symmetry) conformers with a small energy gap (0.1-0.6 kcal/mol). This disjoined substitution pattern necessarily forces delocalization through and around the CPP radial structure. We demonstrate new electronic states from this radial/linear mixing in both the small molecules and the pi extended polymers. Quantum chemical calculations reveal these electronic processes to arise from multiple operative radial/linear conjugation pathways, as the disjoint pattern results in both ortho and meta connections to the CPP ring. Furthermore, these results affirm the unique nature of hybrid radial and linear pi electron delocalization operative in these new conjugation pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Stepwise deprotonation of truxene: structures, metal complexation, and charge-dependent optical properties

As a planar subunit of C 60 -fullerene, truxene (C 27 H 18 ) represents a highly symmetrical rigid hydrocarbon with strong blue emission. Herein, we used truxene as a model to investigate the chemical reactivity of a fullerene fragment with alkali metals. Monoanion, dianion, and trianion products with different alkali metal counterions were crystallized and fully characterized, revealing the core curvature dependence on charge and alkali metal coordination. Moreover, a proton nuclear magnetic resonance study coupled with computational analysis demonstrated that deprotonation of the aliphatic CH 2 segments introduces aromaticity in the five-membered rings. Importantly, the UV-vis absorption and photoluminescence of truxenyl anions with different charges reveal intriguing charge-dependent optical properties, implying variation of the electronic structure based on the deprotonation process. An increase in aromaticity and π-conjugation yielded a red shift in the absorption and photoluminescent spectra; in particular, large Stokes shifts were observed in the truxenyl monoanion and dianion with high emission quantum yield and time of decay. Overall, stepwise deprotonation of truxene provides the first crystallographically characterized examples of truxenyl anions with three different charges and charge-dependent optical properties, pointing to their potential applications in carbon-based functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Finite-difference time-domain methods

The finite-difference time-domain (FDTD) method is a widespread numerical tool for full-wave analysis of electromagnetic fields in complex media and for detailed geometries. Applications of the FDTD method cover a range of time and spatial scales, extending from subatomic to galactic lengths and from classical to quantum physics. Technology areas that benefit from the FDTD method include biomedicine — bioimaging, biophotonics, bioelectronics and biosensors; geophysics — remote sensing, communications, space weather hazards and geolocation; metamaterials — sub-wavelength focusing lenses, electromagnetic cloaks and continuously scanning leaky-wave antennas; optics — diffractive optical elements, photonic bandgap structures, photonic crystal waveguides and ring-resonator devices; plasmonics — plasmonic waveguides and antennas; and quantum applications — quantum devices and quantum radar. This Primer summarizes the main features of the FDTD method, along with key extensions that enable accurate solutions to be obtained for different research questions. Additionally, hardware considerations are discussed, plus examples of how to extract magnitude and phase data, Brillouin diagrams and scattering parameters from the output of an FDTD model. Furthermore, the Primer ends with a discussion of ongoing challenges and opportunities to further enhance the FDTD method for current and future applications.

42 ENGINEERING↗
DOE OSTI2021

A High Energy X-ray Diffraction Study of Amorphous Indomethacin

Amorphous pharmaceuticals often possess a wide range of molecular conformations and bonding arrangements. The x-ray pair distribution function (PDF) method is a powerful technique for the characterization of variations in both intra-molecular and inter-molecular packing arrangements. Here, the x-ray PDF of amorphous Indomethacin is shown to be particularly sensitive to the preferred orientations of the chlorobenzyl ring found in isomers in the crystalline state. In some cases, the chlorobenzyl ring has no preferred torsional angle in the amorphous form, while in others evidence of distinct isomer orientations are observed. Amorphous samples with no preferred torsion angles of the chlorobenzyl ring are found to favor enhanced inter-molecular hydrogen bonding, and this is reflected in the intensity of the first sharp diffraction peak. These significant variations in structure rule out amorphous Indomethacin as a possible standard for x-ray PDF measurements. At high humidity, time resolved PDF's for >40 h reveal water molecules forming hydrogen bonds with Indomethacin molecules. Finally, a simple linear hydrogen bond model indicates that water molecules in the wet amorphous form have similar hydrogen bond strengths to those found between Indomethacin dimers or chains in the dry amorphous form.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Late Life Supplementation of 25‐Hydroxycholesterol Reduces Aortic Stiffness and Cellular Senescence in Mice

ABSTRACT Stiffening of the aorta is a key antecedent to cardiovascular diseases (CVD) with aging. Age‐related aortic stiffening is driven, in part, by cellular senescence—a hallmark of aging defined primarily by irreversible cell cycle arrest. In this study, we assessed the efficacy of 25‐hydroxycholesterol (25HC), an endogenous cholesterol metabolite, as a naturally occurring senolytic to reverse vascular cell senescence and reduce aortic stiffness in old mice. Old (22–26 months) p16‐3MR mice, a transgenic model allowing for genetic clearance of p16‐positive senescent cells with ganciclovir (GCV), were administered vehicle, 25HC, or GCV to compare the efficacy of the experimental 25HC senolytic versus genetic clearance of senescent cells. We found that short‐term (5d) treatment with 25HC reduced aortic stiffness in vivo, assessed via aortic pulse wave velocity (p = 0.002) to a similar extent as GCV. Ex vivo 25HC exposure of aorta rings from the old p16‐3MR GCV‐treated mice did not further reduce elastic modulus (measure of intrinsic mechanical stiffness), demonstrating that 25HC elicited its beneficial effects on aortic stiffness, in part, through the suppression of excess senescent cells. Improvements in aortic stiffness with 25HC were accompanied by favorable remodeling of structural components of the vascular wall (e.g., lower collagen‐1 abundance and higher α‐elastin content) to a similar extent as GCV. Moreover, 25HC suppressed its putative molecular target CRYAB, modulated CRYAB‐regulated senescent cell anti‐apoptotic pathways, and reduced markers of cellular senescence. The findings from this study identify 25HC as a potential therapy to target vascular cell senescence and reduce age‐related aortic stiffness.

Cell Biology↗
DOE OSTI2020

Measuring the muon precession frequency in the E989 Fermilab g-2 experiment

Since more than 50 years the electron and muon anomalies, $a_e$ and $a_\mu$, defined in terms of the gyromagnetic factor $g_i$ for particle $i$ as $a_i=(g_i-2)/2$, have provided a deep insight into the quantum structure of elementary particles.They have been, and continue to be, a milestone for the development of the Standard Model of Particle Physics against which all new theories have to be compared.For almost 20 years, the experimental value of $a_\mu$ has shown a tantalizing discrepancy of more than $3 \sigma$ from the theoretical prediction making it mandatory for experimentalists to improve the current result, dominated by the E821 experiment at BNL\cite{BNL}. The Muon $g-2$ E989 experiment at Fermilab will use the same storage ring technique used at BNL, and previously in the CERN-III experiment, with the goal of decreasing by a factor of 4 the current error on $a_\mu$, which will allow for a finer comparison with the theoretical prediction. E989 started collecting data in winter 2018 accumulating, in the period April-July 2018 (Run1) almost twice the statistics of the previous experiment (before application of data quality cuts). In this document, the experiment will be briefly described, underlying the improvements which will allow to reduce the systematic error, and some preliminary result will be shown.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Autoencoder Based Analysis of RF Parameters in the Fermilab Low Energy Linac

Machine learning (ML) has the potential for significant impact on the modeling, operation, and control of particle accelerators due to its ability to model nonlinear behavior, interpolate on complicated surfaces, and adapt to system changes over time. Anomaly detection in particular has been highlighted as an area where ML can significantly impact the operation of accelerators. These algorithms work by identifying subtle behaviors of key variables prior to negative events. Efforts to apply ML to anomaly detection have largely focused on subsystems such as RF cavities, superconducting magnets, and losses in rings. However, dedicated efforts to understand how to apply ML for anomaly detection in linear accelerators have been limited. In this paper the use of autoencoders is explored to identify anomalous behavior in measured data from the Fermilab low-energy linear accelerator.

Edelen, Jonathan P. (ORCID:0000000215180652)↗
DOE OSTI2020

Photometric Analyses of Saturn’s Small Moons: Aegaeon, Methone, and Pallene Are Dark; Helene and Calypso Are Bright

We examine the surface brightnesses of Saturn’s smaller satellites using a photometric model that explicitly accounts for their elongated shapes and thus facilitates comparisons among different moons. Analyses of Cassini imaging data with this model reveal that the moons Aegaeon, Methone, and Pallene are darker than one would expect given trends previously observed among the nearby mid-sized satellites. On the other hand, the trojan moons Calypso and Helene have substantially brighter surfaces than their co-orbital companions Tethys and Dione. These observations are inconsistent with the moons’ surface brightnesses being entirely controlled by the local flux of E-ring particles, and therefore strongly imply that other phenomena are affecting their surface properties. The darkness of Aegaeon, Methone, and Pallene is correlated with the fluxes of high-energy protons, implying that high-energy radiation is responsible for darkening these small moons. Meanwhile, Prometheus and Pandora appear to be brightened by their interactions with the nearby dusty F ring, implying that enhanced dust fluxes are most likely responsible for Calypso’s and Helene’s excess brightness. However, there are no obvious structures in the E ring that would preferentially brighten these two moons, so there must either be something subtle in the E-ring particles’ orbital properties that leads to asymmetries in the relevant fluxes, or something happened recently to temporarily increase these moons’ brightnesses.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Dual‐Scale Nanostructures via Evaporative Assembly

Abstract Dual‐scale hierarchical structures with regular microscale patterns and varying degree of nanoscale crystalline order are synthesized on physically and chemically homogeneous substrates by evaporative self‐assembly with a suspension of DNA‐functionalized nanoparticles (NPs) with a charged core shell. For a certain NP concentration range, periodic concentric rings in a stripe‐like micropattern are produced over macroscale surface areas by an NP monolayer with hexagonal lattice structure at the nanoscale. The stripe width, spacing, and nanoparticle ordering can be controlled by varying the NP concentration. The results indicate that the interplay between “stick‐slip” motion of the droplet contact line and coulombic and steric NP interactions control the formation of the observed structures. A simple analytical model is proposed to account for the experimental observations and guide the future design of different nanostructure morphologies. This work demonstrates a simple cost‐effective mask‐free method for fabricating large‐area nanostructured 2D materials and metasurfaces for applications ranging from energy conversion/storage to optoelectronics and nanophotonics.

Srivastava, Sunita↗
DOE OSTI2026

Quantifying the Influences of Epoxide Binding in Epoxide/CO 2 Ring Opening Copolymerization Catalysis

Understanding and predicting the effect of epoxide structure on the rate of polymerization in epoxide/CO 2 ring opening copolymerization catalysis is a long-standing challenge. Here, a known highly active Co(III)K(I) catalyst is used to investigate the influences of six different epoxides' binding strengths on their rates of copolymerization. Since calculations and experiments indicate that studying the catalytically relevant Co(III)−epoxide adduct directly is experimentally challenging, epoxide−catalyst binding interactions are quantified using a Co(II)K(I) complex to model the key catalytic intermediate. Epoxide−catalyst coordination is investigated using UV−vis spectroscopy titrations which provide fast and effective determination of association or binding constants. The epoxide−catalyst equilibrium constants show a clear exponential correlation with copolymerization rates and a new catalyst performance linear free energy relationship is revealed. Epoxides exhibiting stronger catalyst binding constants show higher copolymerization rates. The structure−activity correlation is consistent with the polymerization kinetics, mechanism and DFT calculations. Both the methods to investigate epoxide−catalyst coordination and the linear free energy relationship are shown to apply to the series of six epoxides and a second Co(III)K(I) catalyst. These structure− performance relationships are likely applicable to other transition metal catalysts and should expedite future epoxide and catalyst selection to make useful poly(carbonate) materials.

catalysts↗
DOE OSTI2023

Millimeter observational signatures of flares in magnetically arrested black hole accretion models

In general relativistic magnetohydrodynamic (GRMHD) simulations, accreted magnetic flux on the black hole horizon episodically decays, during which magnetic reconnection heats up the plasma near the horizon, potentially powering high-energy flares like those observed in M87* and Sgr A*. We study the mm observational counterparts of such flaring episodes in very high resolution GRMHD simulations. The change in 230 GHz flux during the expected high energy flares depends primarily on the efficiency of accelerating γ ≳ 100 (T e ≳ 10 11 K) electrons. For models in which the electrons are heated to T e ∼ 10 11 K during flares, the hot plasma produced by reconnection significantly enhances 230 GHz emission and increases the size of the 230 GHz image. By contrast, for models in which the electrons are heated to higher temperatures (which we argue are better motivated), the reconnection-heated plasma is too hot to produce significant 230 GHz synchrotron emission, and the 230 GHz flux decreases during high energy flares. We do not find a significant change in the mm polarization during flares as long as the emission is Faraday thin. We also present expectations for the ring-shaped image as observed by the Event Horizon Telescope during flares, as well as multiwavelength synchrotron spectra. Our results highlight several limitations of standard post-processing prescriptions for the electron temperature in GRMHD simulations. We also discuss the implications of our results for current and future observations of flares in Sgr A*, M87*, and related systems. Appendices contain detailed convergence studies with respect to resolution and plasma magnetization.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Dissociative Recombination of Cold HeH + Ions

The HeH + cation is the simplest molecular prototype of the indirect dissociative recombination (DR) process that proceeds through electron capture into Rydberg states of the corresponding neutral molecule. This Letter develops the first application of our recently developed energy-dependent frame transformation theory to the indirect DR processes. The theoretical model is based on the multichannel quantum-defect theory with the vibrational basis states computed using exterior complex scaling of the nuclear Hamiltonian. The ab initio electronic R-matrix theory is adopted to compute quantum defects as functions of the collision energy and of the internuclear distance. The resulting DR rates are convolved over the beam energy distributions relevant to a recent experiment at the Cryogenic Storage Ring, giving good agreement between the experiment and the theory.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Delivery Ring Spill Characterization and Impulse Study

High-intensity particle physics experiments require uniform beam extraction to prevent instantaneous rate spikes from overwhelming detector systems. By analyzing accelerator parameters and extracted beam dynamics, we directly inform spill regulation systems that make real-time adjustments to minimize non-uniformity. This Department of Energy Visiting Faculty Program project transitioned from characterizing Main Injector half-integer slow extraction for SpinQuest to Delivery Ring third-integer slow extraction for Mu2e. Working alongside the Fast Adaptive Neural Control (FANC) group, we developed an automated pipeline that aligns asynchronous instrument channels, embeds quality metrics, and isolates clean spill populations. Analyzing baseline spills alongside a dedicated quadrupole impulse study allowed us to quantify noise structures while mapping time-varying beam response and transit-delay dynamics. These empirical measurements directly ground digital twin models, supporting FANC’s deployment of real-time, FPGA-based neural network controllers in the Mu2e Spill Regulation System.

Dolen, James William [Purdue U., West Lafayette] (↗
DOE OSTI2023

Beam dynamics corrections in the measurement of the anomalous precession frequency at the Muon $g-2$ experiment at Fermilab

The Muon $g-2$ experiment at Fermilab (E989) aims to measure the anomalous magnetic moment of the muon with an accuracy of 140 ppb (parts per billions). This accuracy, obtained by adding in quadrature a statistical and a systematic contribution of comparable value (100 ppb), will allow to reduce the experimental uncertainty (from the previous E821 experiment at BNL \cite{bnl}) of a factor of 4, and represents one of the most precise tests of the Standard Model (SM) theory of elementary particles. The first result on the Run-1 dataset \cite{prl} was released on April 7, 2021, showing a very good agreement with the previous result from BNL experiment, with a slightly better uncertainty. The corresponding experimental average increases the significance of the discrepancy between the measured and Standard Model prediction of 4.2$\sigma$ \cite{white_paper}.\\ \noindent The measured quantity is the muon magnetic anomaly a$_\mu$=$\frac{g_\mu-2}{2}$ where g$_\mu$ is the gyromagnetic factor of the muon. Dirac's equation predicts g$_\mu$ = 2, while radiative corrections, dominated by the QED contribution due to an exchange of a virtual photon, causes a per-mille correction on this quantity. By including all the SM contributions, a$_\mu$ is known at 370 ppb. The E989 experiment measures $a_\mu$ injecting positive muons with momentum of 3.1 GeV/$c$ polarized longitudinally in bunches (called $fills$) with an average rate of 12 Hz, in a storage ring of 14 meters diameter. Due to the parity violation in the weak muon decay, high energy positrons produced are emitted preferably in the muon's spin direction. By counting the number of positrons with energy greater then 1.7 GeV in function of the time, the frequency precession of the muon spin is measured, that together with the measurement of the magnetic field, allows to extract $a_\mu$. The positrons are detected with 24 electromagnetic calorimeters, that measure the energy and the arrival time of the positrons, each made of 54 crystals of lead fluoride (PbF$_2$) read by silicon photomultipliers (SiPM). Together with calorimeters, two tracking detectors are used to make non-destructive measurements of the muon beam characteristic by reconstructing the muon decay position extrapolating backward the decay positrons. The knowledge of the beam motion inside the ring plays a fundamental role in the analysis of $a_{\mu}$, where the measured anomalous precession frequency $\omega_a$ must be corrected for four main beam dynamics effects. A first correction is associated with the presence of an electric field responsible of the vertical focusing on the storage ring, where vertical direction is orthogonal to the orbit and horizontal direction is along the storage ring radius. Due to the oscillations in the vertical direction, the so called vertical betatron oscillations, a second correction is necessary to account for an average angle associated with the muon motion off the ideal orbit. A third correction is caused by lost muons in the ring which have a different spin phase at the injection respect to the decay ones. Finally, due to the correlation between the vertical and horizontal beam motion of the muons and the acceptance of the calorimeter, a correction (called ``phase-acceptance") arises. In Run1, due to the presence of two damaged resistors in one electrostatic quadrupole, this correction had a prominent role. The replacement of the damaged resistors before Run2 decreased this effect by one order of magnitude, and a further reduction in Run-3 was provided by an improved orbit.\\ \noindent The work of this Thesis focuses on the beam dynamics corrections on $\omega_a$. Due to the prominent role in Run-1 a special attention has been put to the phase-acceptance correction\footnote{The effect of this correction on the E821 BNL measurement of the $g-2$ has been evaluated to be within the quoted systematic error.}. Chapter \ref{ch:anomalous_magnetic_moment} introduces the anomalous magnetic moment of the muon. Chapter \ref{ch:early_experiment} describes the history of the Muon $g-2$ experiments. Chapter \ref{ch:theory} discusses the Standard Model prediction and possible new physics scenario. Chapter \ref{ch:muon_g2_experiment} describes the E989 experiment, whose experimental technique and the apparatus are discussed focusing on the improvements needed to reach the final goal on $a_\mu$ measurement. The original work of the Thesis is discussed in the last 5 chapters. Chapter \ref{ch:experiment_technique} presents the analysis technique to extract $\omega_a$, Chapter \ref{ch:beam_dynamics} describes the beam dynamics in the E989 experiment, Chapter \ref{ch:beam_dynamics_correction} discusses the beam dynamics correction to $\omega_a$, and Chapter \ref{sec:pa_corr} focuses on the phase acceptance correction. Finally Chapter \ref{ch:run23_analysis_improvements} contains the Run-2/3 improvements which are expected to allow for an increased precision ons the beam dynamics co...

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2026

Microcanonical Kinetics of Water-Mediated Proton Transfer in 4ABAH + ·(H 2 O) n = 4–6 Clusters (ABA = Aminobenzoic Acid): A Model System for Size-Dependent Relaxation to Ergodic Behavior

Here, we leverage the unique properties of the 4ABAH + · (H 2 O) n clusters (ABA = 4-aminobenzoic acid, n = 4−6) to quantitatively address how a finite, isolated system evolves into an ergodic condition starting from localized arrangements in configuration space. This system adopts two distinct structural isomers in which water molecules cluster around the cationic centers of its two protomers with widely separated positive charge centers. These isomers arise from excess proton attachment to either the acid (O) or amino (N) group on opposite sides of the benzene ring. Both forms are captured and kinetically trapped using cryogenic ion methods and then selectively vibrationally excited through their mutually exclusive IR bands involving NH and OH stretching fundamentals. Because the IR excitation lies below the water binding energy, the system can evolve to explore slow, rare events that lead to the interconversion between the two isomers. The rates of these intracluster reactions are determined by using a pump−probe scheme involving ∼5 ns IR pump and UV probe lasers. The rates occur on the microsecond time scale, leading to steady state populations of the isomers, thus revealing the cluster size-dependent fractionation between the two species at microcanonical equilibrium. The steady state distributions are correlated with the expected trend in the cluster size-dependent reaction energetics, which are in turn consistent with changes in the relative densities of states of the two species. These results thus provide an unusually clear example in which complex, protic-solvent-mediated chemical transformations are captured within a finite system at a precisely determined internal energy.

Rana, Abhijit [Yale Univ., New Haven, CT (United S↗