Caught in the act: real-time observation of the solvent response that promotes excited-state proton transfer in pyranine
Observation of photoinduced excited proton transfer (ESPT) reactions: from the onset of proton transfer up to thermalization.
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Observation of photoinduced excited proton transfer (ESPT) reactions: from the onset of proton transfer up to thermalization.
Abstract Metasurfaces (MSs), or surfaces consisting of engineered spatially oriented sub-wavelength elements—also known as meta-atoms—are quickly becoming a burgeoning field of interest due to their seemingly unparalleled control over the propagation of light. This article will discuss the emergence of a MS technology that is based on dewetting thin metal films to form dry etching masks for MS fabrication. The novelty this process presents is the ability to spatially vary mask features—which translates into spatially varying index of the finished surface—in a way that, rather than writing subwavelength elements one-by-one, writes entire areas at once to provide a route to easily scale the process up to meter-sized optics. Glass-engraved MSs have shown to be laser damage resistant, with damage thresholds close to the parent substrate damage thresholds. Furthermore, these surfaces have proven to be mechanically durable and capable of handling normal loads two orders of magnitude higher than that of an average fingerprint pressure. This indicates that accidental handling contact is not detrimental to the MS optical performance. Also discussed are the foreseeable technological challenges, potential solutions for those obstacles, and some currently unexplored directions for future efforts.
Abstract Potassium dihydrogen phosphate (KDP) and its deuterated analog (DKDP) are unique nonlinear optical materials for high power laser systems. They are used widely for frequency conversion and polarization control by virtue of the ability to grow optical-quality crystals at apertures suitable for fusion-class laser systems. Existing methods for freeform figuring of KDP/DKDP optics do not produce surfaces with sufficient laser-induced–damage thresholds (LIDT’s) for operation in the ultraviolet portion of high-peak-power laser systems. In this work, we investigate fluid jet polishing (FJP) using a nonaqueous slurry as a sub-aperture finishing method for producing freeform KDP surfaces. This method was used to selectively polish surface areas to different depths on the same substrate with removals ranging from 0.16 μm to 5.13 μm. The finished surfaces demonstrated a slight increase in roughness as the removal depth increased along with a small number of fracture pits. Laser damage testing with 351 nm, 1 ns pulses demonstrated excellent surface damage thresholds, with the highest values in areas devoid of fracture pits. This work demonstrates, for the first time, a method that enables fabrication of a waveplate that provides tailored polarization randomization that can be scaled to meter-sized optics. Furthermore, this method is based on FJP technology that incorporates a nonaqueous slurry specially designed for use with KDP. This novel nonaqueous FJP process can be also used for figuring other types of materials that exhibit similar challenging inherent properties such as softness, brittleness, water-solubility, and temperature sensitivity.
The X-Ray Imaging and Spectroscopy Mission satellite was launched on September 6, 2023 (UT). Its Resolve instrument is a high-resolution X-ray spectrometer enabled by a microcalorimeter array thermally anchored to a 50-mK heat sink. Many sensitive, critical sub-systems comprise Resolve, including a multistage cryogenic cooling system, thin-film aperture filters, low-noise electronics, on-board signal processing, and several sources of X-rays for calibration. We summarize the initial on-orbit power-on and checkout of Resolve that commenced immediately after launch. Soon after launch, the cryocoolers were activated, and their operation was successfully established. On October 9, 2023, the first cycle of the adiabatic demagnetization refrigerator was carried out, bringing the sensors to their steady-state operational temperatures. Following this, the energy resolution at 5.9 keV was successfully measured. The energy scale of the system is highly sensitive to the thermal environment surrounding both the sensors and their analog electronics. Gain correction was performed using reference X-ray lines from onboard calibration sources. To optimize cooler frequency settings, noise spectra were collected across a range of frequencies, and the most suitable frequency pair was selected based on the in-orbit environment. During the final phase of the checkout, an attempt was made to open the gate valve, which is designed to protect the Dewar’s interior from external pressure during ground operations and launch. Unfortunately, this attempt was unsuccessful. As a result, the checkout process was temporarily paused, and a stable operational strategy was subsequently developed to enable Resolve to function effectively with the gate valve remaining closed.
We present measurements of the large-scale cosmic-ray anisotropies in right ascension, using data collected by the surface detector array of the Pierre Auger Observatory over more than 14 years. We determine the equatorial dipole component, $\vec{d}_\perp$, through a Fourier analysis in right ascension that includes weights for each event so as to account for the main detector-induced systematic effects. For the energies at which the trigger efficiency of the array is small, the ``East-West'' method is employed. Besides using the data from the array with detectors separated by 1500 m, we also include data from the smaller but denser sub-array of detectors with 750 m separation, which allows us to extend the analysis down to $\sim 0.03$ EeV. The most significant equatorial dipole amplitude obtained is that in the cumulative bin above 8~EeV, $d_\perp=6.0^{+1.0}_{-0.9}$%, which is inconsistent with isotropy at the 6$\sigma$ level. In the bins below 8 EeV, we obtain 99% CL upper-bounds on $d_\perp$ at the level of 1 to 3 percent. At energies below 1 EeV, even though the amplitudes are not significant, the phases determined in most of the bins are not far from the right ascension of the Galactic center, at $\alpha_{\rm GC}=-94^\circ$, suggesting a predominantly Galactic origin for anisotropies at these energies. The reconstructed dipole phases in the energy bins above 4 EeV point instead to right ascensions that are almost opposite to the Galactic center one, indicative of an extragalactic cosmic ray origin.
The observation of primordial B modes in cosmic microwave background (CMB) polarisation data represents the main scientific goal of most of the future CMB experiments. This signal is predicted to be much lower than polarised Galactic emission (foregrounds) in any region of the sky, pointing to the need for effective component separation methods. Aims. Among all the techniques, the blind Needlet Internal Linear Combination (NILC) is of great relevance given our current limited knowledge of the B-mode foregrounds. In this work, we explore the possibility of employing NILC for the analysis of B modes reconstructed from partial-sky data, specifically addressing the complications that such an application yields such as E–B leakage, needlet filtering, and beam convolution. We consider two complementary simulated datasets of future experiments: the balloon-borne Short Wavelength Instrument for the Polarisation Explorer (SWIPE) of the Large Scale Polarisation Explorer, which targets the observation of both reionisation and recombination peaks of the primordial CMB B-mode angular power spectrum, and the ground-based Small Aperture Telescope of Simons Observatory, which, instead, is designed to observe only the recombination bump at ℓ ~ 80. We assessed the performance of the following two alternative techniques to correct for the CMB E–B leakage: the recycling technique and the Zhao-Baskaran method. We find that both techniques reduce the E–B leakage residuals at a negligible level given the sensitivity of the considered experiments, except for the recycling method in the SWIPE footprint at ℓ < 20. Thus, we implemented two extensions of the pipeline, the iterative B decomposition and the diffusive inpainting, which enabled us to recover the input CMB B-mode power for ℓ ≥ 5. For the considered experiments, we demonstrate that needlet filtering and beam convolution do not affect the CMB B-mode reconstruction. Finally, with an appropriate masking strategy, we find that NILC foregrounds subtraction allows one to achieve sensitivities on the tensor-to-scalar ratio in agreement with the targets of the considered CMB experiments.
An X-pinch load driven by an intense current pulse (>100 kA in ~100 ns) can result in the formation of a small radius, runaway compressional micro-pinch. A micro-pinch is characterized by a hot (>1 keV), current-driven (>100 kA), high-density plasma column (near solid density) with a small neck diameter (1–10 µm), a short axial extent (<1 mm), and a short duration (≲1 ns). With material pressures often well into the multi-Mbar regime, a micro-pinch plasma often radiates an intense, sub-ns burst of sub-keV to multi-keV x rays. A low-density coronal plasma immediately surrounding the dense plasma neck could potentially shunt current away from the neck and thus reduce the magnetic drive pressure applied to the neck. Here, to study the current distribution in the coronal plasma, a Faraday rotation imaging diagnostic (1064 nm) capable of producing simultaneous high-magnification polarimetric and interferometric images has been developed for the MAIZE facility at the University of Michigan. Designed with a variable magnification (1–10×), this diagnostic achieves a spatial resolution of ~35 µm, which is useful for resolving the ~100-μm-scale coronal plasma immediately surrounding the dense core. This system has now been used on a reduced-output MAIZE (100–200 kA, 150 ns) to assess the radial distribution of drive current immediately surrounding the dense micro-pinch neck. The total current enclosed was found to increase as a function of radius, r, from a value of ≈ 50 ± 25 kA at r ≈ 140 µm (at the edge of the dense neck) to a maximal value of ≈150 ± 75 kA for r ≥ 225 µm. This corresponds to a peak magnetic drive pressure of ≈75 ± 50 kbar at r ≈ 225 µm. The limitations of these measurements are discussed in the paper.
Geostationary infrared satellite observations are spatially dense [< 1/(20 km)2] and temporally frequent (< 1/hour). These suggest the possibility of using these observations to constrain sub-synoptic features over data sparse regions, such as tropical oceans. In this study, the potential impacts of assimilating water vapor channel brightness temperature (WV-BT) observations from the geostationary Meteorological Satellite 7 (Meteosat-7) on tropical convection analysis and prediction were systematically examined through a series of ensemble data assimilation experiments. WV-BT observations were assimilated hourly into convection-permitting ensembles using Penn State’s ensemble square root filter (EnSRF). Comparisons against independently observed Meteosat-7 window channel brightness temperature (Window-BT) show that the assimilation of WV-BT generally improved the intensities and locations of large-scale cloud patterns at spatial scales larger than 100 km. However, comparisons against independent soundings indicate that the EnSRF analysis produced a much stronger dry bias than the no data assimilation experiment. This strong dry bias is associated with the use of the simulated WV-BT from the prior mean during the EnSRF analysis step. A stochastic variant of the ensemble Kalman filter (NoMeanSF) is proposed. The NoMeanSF algorithm was able to assimilate the WV-BT without causing such a strong dry bias and the quality of the analyses’ horizontal cloud pattern is similar to EnSRF’s analyses. Finally, deterministic forecasts initiated from the NoMeanSF analyses possess better horizontal cloud patterns above 500 km than those of the EnSRF. These results suggest that it might be better to assimilate all-sky WV-BT through the NoMeanSF algorithm than EnSRF algorithm.
Abstract We consider a $$U(1)_{B-L}$$ U ( 1 ) B - L model with a $$Z^\prime $$ Z ′ portal Dirac fermion dark matter (DM) $$\chi $$ χ of low mass which couples very weakly to the $$B - L$$ B - L gauge boson $$Z^\prime $$ Z ′ . An arbitrary $$B-L$$ B - L charge $$Q\ne \pm 1, \pm 3$$ Q ≠ ± 1 , ± 3 of the DM $$\chi $$ χ ensures its stability. Motivated by the sensitivity reach of forthcoming “Lifetime Frontier” experiments, we focus on the $$Z^\prime $$ Z ′ mass, $$m_{Z^\prime }$$ m Z ′ , in the sub-GeV to few GeV range. To evaluate the DM relic abundance, we examine both the freeze-out and freeze-in DM scenarios. For the freeze-out scenario, we show that the observed DM abundance is reproduced near the $$Z^\prime $$ Z ′ resonance, $$m_\chi \simeq m_{Z^\prime }/2$$ m χ ≃ m Z ′ / 2 , where $$m_\chi $$ m χ is the DM mass. For the freeze-in scenario, we focus on $$m_\chi \ll m_{Z^\prime }$$ m χ ≪ m Z ′ . We show that for a fixed value of $$m_{Z^\prime }$$ m Z ′ , $$g_{BL}$$ g BL values roughly scale as 1/ Q to reproduce the observed DM abundance. For various Q values in the range between $$10^{-6}$$ 10 - 6 and $$10^2$$ 10 2 , we show that the gauge coupling values $$g_{BL}$$ g BL needed to reproduce the observed DM abundance lie in the search reach of future planned and/or proposed experiments such as FASER, Belle-II, LDMX, and SHiP. In the freeze-in case, the Q values to realize observable $$g_{BL}$$ g BL values are found to be much smaller than that in the freeze-out case.
We use the latest measurements of the Milky Way satellite population from the Dark Energy Survey and Pan-STARRS1 to infer the most stringent astrophysical bound to date on velocity-dependent interactions between dark matter particles and protons. We model the momentum-transfer cross section as a power law of the relative particle velocity v with a free normalizing amplitude, σ MT = σ 0 v n , to broadly capture the interactions arising within the nonrelativistic effective theory of dark matter–proton scattering. The scattering leads to a momentum and heat transfer between the baryon and dark matter fluids in the early universe, ultimately erasing structure on small physical scales and reducing the abundance of low-mass halos that host dwarf galaxies today. From the consistency of observations with the cold collisionless dark matter paradigm, using a new method that relies on the most robust predictions of the linear perturbation theory, we infer an upper limit on σ0 of 1.4 × 10 -23 , 2.1 × 10 -19 , and 1.0 × 10 -12 cm 2 , for interaction models with n = 2, 4, and 6, respectively, for a dark matter particle mass of 10 MeV. These results improve observational limits on dark matter–proton scattering by orders of magnitude and thus provide an important guide for viable sub-GeV dark matter candidates.
Subgraph isomorphism is a pattern-matching algorithm widely used in many domains such as chem-informatics, bioinformatics, databases, and social network analysis. It is computationally expensive and is a proven NP-hard problem. The massive parallelism offered by the GPU hardware is well suited for solving the subgraph isomorphism. However, current GPU implementations are far from the achievable performance. Moreover, the enormous memory requirement of current approaches limits the problem size that can be handled. This work analyzes the fundamental challenges associated with processing the subgraph isomorphism on GPUs and develops an efficient GPU hardware-aware implementation. We also develop a new GPU-friendly trie-based data structure to drastically reduce the intermediate storage space requirement. Hence, our approach runs larger benchmarks than the competitors. We also develop the first distributed sub-graph isomorphism algorithm for GPUs. Our experimental evaluation section demonstrates the efficacy of our approach by comparing the execution time and number of cases that we can handle against the state-of-the-art GPU implementations.
We report on several efforts to search for physics beyond the standard model of particle physics at broad energy scales. The Mu2e experiment at Fermilab will search for charged lepton flavor violation via the muon to electron conversion process, which is suppressed in the Standard Model. Mu2e will be operated at a low energy, yet can probe New Physics at very high mass scales (O(1e3 - 1e4 ) TeV). At high energies, the CMS experiment at the CERN LHC continues to deliver an impressive suite of Standard Model measurements and limits on a variety of New Physics signatures. Mu2e is under construction and slated to collect its first physics data in the coming years. This thesis describes work done during the construction phase of Mu2e and focuses on two critical areas: magnetic field modeling and statistical analysis. We describe a novel method for field modeling which we validate using a simulated dataset representing the expected magnetic field in the Detector Solenoid. This method blends a standard least-squares fitting technique that utilizes physically motivated analytical model functions with a novel physics informed network that is constructed to obey Maxwell’s equations. We show the technique can model the field with an accuracy of 10−7 despite the presence of injected noise in the pseudo-measurements at the 10−5 level. We then present preliminary results of the calibration of 3D Hall probes at the sub-10−4 level. These probes will be used to directly measure the Mu2e Detector Solenoid magnetic field on a sparse grid; these measurements serve as the input to the field model fitting. Finally, we describe the first implementation of both an unbinned shape analysis and a Bayesian interpretation applied to Mu2e pseudo-data. Up to 20% tighter limits can be set by the shape analysis compared to a standard cut & count analysis. The AlCap experiment collected data at PSI in 2015 to measure several important quantities related to nuclear muon capture on an aluminum target, which is a significant background process for Mu2e. The neutron emission from muon capture can introduce background hits in the Mu2e detectors and can increase radiation damage in various elements of the apparatus. We present measurements of the neutron group fluence and mean neutron multiplicity for muon capture on aluminum nuclei. Finally, we discuss an analysis of triboson production at CMS using an Effective Field Theory framework. Standard Model triboson production, which was first observed at CMS in 2020, has a relatively small cross section and provides direct access to both anomalous triple gauge couplings and quartic gauge couplings. These couplings, interpreted in the Standard Model Effective Field Theory, are studied in the present work. We target the boosted regime where the background rate is low and yields are enhanced when dimension-6 and dimension-8 Wilson coefficients are non-zero. We do not observe an excess in the data and therefore set bounds on the Wilson coefficients. For dimension-6 coefficients the tightest observed (expected) bounds are set on cW /Λ2 where Λ is the mass scale of new physics; the bounds are [−0.13, 0.12] TeV−2 ([−0.12, 0.12] TeV−2 ) at 95% CL. The tightest bounds in dimension-8 are set on fT,0 / Λ4 ; the observed (expected) bounds at 95% CL are [−0.63, 0.69] TeV−4 ([−0.54, 0.62] TeV−4 ). Additional results are presented which include scenarios where multiple Wilson coefficients are non-zero, the application of signal model clipping to address unitarity violation in Effective Field Theories, and a novel template fit developed for easier reinterpretation of our results.
High-speed visible imaging of sub-microsecond electric explosion of wires at the low specific energy deposition threshold reveals three distinct modes of wire failure as capacitor charge voltage and energy deposition are increased. For 100 micron diameter gold-plated tungsten wires of 2 cm length, deposited energies of 1.9 eV/atom produces a liquid column that undergoes hydrodynamic breakup into droplets with radii of order of wire diameter on timescales of 200 μs. Instability growth, column breakup, and droplet coalescence follow classic Rayleigh-Plateau predictions for instability of viscous fluid column. Above 3.2 eV/atom of deposited energy, wires are seen to abruptly transition to an expanding mixture of micron scale liquid-droplets and vapor within one frame (less than 3.33 μs), which has been termed ‘phase explosion’ in literature. Between these two limits, at 2.5 eV/atom of deposited energy, wire radius is unchanged for the first 10 μs before the onset of a rapid expansion and disintegration that resembles homogenous nucleation of mechanically unstable bubbles. Here, thermodynamic calculations are presented that separate cases by temperature obtained during heating: below boiling point, near boiling point, and exceeding boiling point.
Here this paper investigates how the market impact of electricity merchants and uncertainty of wind generation affect their co-optimized scheduling policy, specifically for merchants who have both energy storage and wind plants. In the existing literature, merchants' trading actions are usually assumed not to affect market prices; however, a large-scale energy storage merchant's actions can affect market prices. To this end, we approximate the electricity price by a linear function of the quantity of power traded by the merchant in the reward function to achieve decision-making incorporating the market impact. This paper utilizes the dynamic programming approach to analyze merchants' optimal multi-period decision-making incorporating market impact, uncertain wind generation, and energy storage constraints. First, our results demonstrate that for a merchant with co-located energy storage facilities and wind power plants, the energy storage's feasible state of charge (SOC) range can be segmented into four possible sub-ranges by three analytically developed SOC reference points. The unique optimal trading decision can be achieved by comparing the current energy inventory and the SOC references of the next period. Second, our results show that market impact and uncertainties substantially change the optimal storage scheduling policy by impacting the values of the reference points. To mitigate the negative effect of the merchant's market impact on buying and selling actions, the merchant may reduce the amount of generating or pumping electricity each period to maximize profit. Moreover, we identify and investigate the trade-off between market price and transaction quantity. Our findings provide co-optimized scheduling guidance for electricity merchants with co-located energy storage and renewable power plants systems.
This summarizes technical highlights from the DOE Early Career Project entitled “Understanding the Roles of Cloud Microphysics and Land Surface Coupling Feedbacks in Multi-Scale Predictions of Central US Summer Hydroclimate” led by PI Mike Pritchard at the University of California. The project’s original aims were to investigate trade-offs of cloud superparameterization such as the effects of microphysical assumptions on mesoscale convective systems (Section I) and the representation of land-atmosphere coupling under explicit convection (Section II). Under the same broader theme of water cycle dynamics, superparameterization, and land interaction, the project evolved to further investigate the climate dynamics of irrigation, vegetation and streamflow (Section III), the dynamics of the Madden- Julian Oscillation (Section IV), as well as the use of modern machine learning to replace traditional sub grid approaches for climate simulation (Section V). Twenty peer-reviewed journal publications were produced as a result of this project (Section VI).
ABSTRACT We explore two widely used empirical models for the galaxy–halo connection, subhalo abundance matching (SHAM) and the halo occupation distribution (HOD), and compare them with the hydrodynamical simulation IllustrisTNG (TNG) for multiple statistics quantifying the galaxy distribution at $n_{\rm gal}\approx 1.3\times 10^{-3}\, ({\rm Mpc}\,h^{-1})^{-3}$. We observe that in their most straightforward implementations, both models fail to reproduce the two-point clustering measured in TNG. We find that SHAM models that use the relaxation velocity, Vrelax, and the peak velocity, Vpeak, perform best, and match the clustering reasonably well, although neither captures adequately the one-halo clustering. Splitting the total sample into sub-populations, we discover that SHAM overpredicts the clustering of high-mass, blue, star-forming, and late-forming galaxies and underpredicts that of low-mass, red, quiescent, and early-forming galaxies. We also study various baryonic effects, finding that subhaloes in the dark-matter-only simulation have consistently higher values of their SHAM-proxy properties than their full-physics counterparts. We then consider a 2D implementation of the HOD model augmented with a secondary parameter (environment, velocity anisotropy, σ2Rhalf-mass, and total potential) tuned so as to match the two-point clustering of the IllustrisTNG galaxies on large scales. We analyse these galaxy populations adopting alternative statistical tools such as galaxy–galaxy lensing, void–galaxy cross-correlations, and cumulants of the density field, finding that the hydrodynamical galaxy distribution disfavours σ2Rhalf-mass and the total potential as secondary parameters, while the environment and velocity anisotropy samples are consistent with full physics across all statistical probes examined. Our results demonstrate the power of examining multiple statistics for determining the secondary parameters that are vital for understanding the galaxy–halo connection.
There are a number of current needs in the development of the Pu and Am separations that underpin larger interest areas including nuclear waste issues, nuclear weapons, nuclear forensics, nuclear fuels and similarly related fields. In the large areas of interest, there are a number of sub-fields that include corrosion chemistry, pyrochemistry, solution-phase chemistry, rapid separations, environmental speciation, and other similar efforts. However, in all of the these fields it is important to realize that the underlying chemistry that underpins these efforts is similar in that Pu and Am are bound to ligands that can be in the solid, aqueous, or gas phase and separations occurs due to the preferential binding of the ligand to Pu or Am based on a number of factors that include pH, concentration, oxidation state, etc. In the past, most of the Pu and Am chemistry has occurred in limited scope within universities where micro-scale and bench-top scale chemistry are the dominate investigative theme. At US national laboratory and their international counterparts, larger scale reactions have been attempted such that industrial scale chemistry has been completed. Some of this technology has been harnessed in radiopharmaceuticals and nuclear fuel reprocessing. However, such bench-top research is expensive to due to the safety and security that is concerned when dealing with Pu, and scale-up of reactions is even more resource intensive. In an effort to offset this expensive, it would be of interest to explore the ability to predict selectivity based on the computational modeling of actinide chemistry. This has historically been limited by the abilities of large supercomputers, but with the emphasis on developing exascale computers within the US and similar efforts by other countries this predictive modeling has potential to produce significant results that would yield improved understanding of actinide chemistry.
This study reports the thickness scaling of sputtered ferroelectric Zn 0.61 Mg 0.39 O (ZMO) thin films down to 43 nm. Encapsulated IrO 2 /ZMO/Ir capacitors exhibited switchable polarizations exceeding 50 μC cm −2 and coercive fields that increased from 3.9 to 4.4 MV cm −1 as the thickness decreased. Switching kinetics are best described by the simultaneous non-linear nucleation and the growth model. Bimodal switching is prevalent at low thicknesses, with the fastest switching times measured to be approximately 400 ns. Device encapsulation made ZMO switching kinetics more abrupt, potentially due to changes in the concentration of atmosphere-induced defects such as hydroxides. These results demonstrate stable ferroelectricity and sub-microsecond switching in sub-50 nm wurtzite ZMO, highlighting its potential as a low-voltage ferroelectric for integrated nonvolatile memory applications.