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At least 199 records · Page 11

Helium droplet infrared spectroscopy of the butyl radicals

Butyl radicals (n-, s-, i-, and tert-butyl) are formed from the pyrolysis of stable precursors (1-pentyl nitrite, 2-methyl-1-butyl nitrite, isopentyl nitrite, and azo-tert-butane, respectively). The radicals are doped into a beam of liquid helium droplets and probed with infrared action spectroscopy from 2700 to 3125 cm -1 , allowing for a low temperature measurement of the CH stretching region. The presence of anharmonic resonance polyads in the 2800–3000 cm -1 region complicates its interpretation. To facilitate spectral assignment, the anharmonic resonances are modeled with two model Hamiltonian approaches that explicitly couple CH stretch fundamentals to HCH bend overtones and combinations: a VPT2+K normal mode model based on coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)] quartic force fields and a semi-empirical local mode model. Both of these computational methods provide generally good agreement with the experimental spectra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

BD+14°3061: A Luminous Yellow Post-AGB Star in the Galactic Halo

I report the discovery that the ninth-mag Galactic-halo star BD+14°3061 is a member of the rare class of luminous metal-poor “yellow post-AGB” stars. Its Gaia DR2 parallax implies an absolute magnitude of M V = -3.44 ± 0.27, and it is a very high-velocity star moving in a retrograde Galactic orbit. BD+14°3061 is a field analog of the half-dozen yellow PAGB stars known in Galactic globular clusters, which have closely similar absolute magnitudes. These objects are the visually brightest members of old stellar populations; their apparently narrow luminosity function makes them potentially useful as Population II standard candles. The spectral-energy distribution of BD+14°3061 out to 22 μm shows no evidence for circumstellar dust. The star is a low-amplitude semiregular pulsating variable, with typical periods of 30–32 days. A radial-velocity study suggests that it is a spectroscopic binary with a period of 429.6 days, making it similar to known binary yellow PAGB stars such as HD 46703 and BD+39°4926.

79 ASTRONOMY AND ASTROPHYSICS↗

Radial Profiles of the Binary Fraction in Elliptical Galaxies

The radial profile of the binary fraction may vary with environment and is of significant importance for studying the formation mechanisms of binary stars and their dynamical evolution within globular clusters and galaxies. However, existing studies remain limited to the Milky Way and its neighboring galaxies. Leveraging the method proposed by Zhang et al. for estimating the variation in the binary fraction from integrated spectral features, we analyze a sample of 513 elliptical galaxies drawn from the Mapping Nearby Galaxies at Apache Point Observatory survey to measure their radial binary fraction profiles. Our results show that after accounting for the effect induced by radial variations in the stellar population (SP), the median SP-subtracted binary fraction, $r^{\textrm{med}}_{\textrm{b,sub}}$, becomes approximately flat. For nearly all elliptical galaxies in our sample, the variation in the binary fraction relative to the galaxy center at 1R e is less than 5%. No clear correlation is found between the ​​​​​gradient of the binary fraction and the gradients of the SP properties. Moreover, we also compare differences between ultraviolet (UV) upturn and non-UV upturn galaxies. The overall binary fraction profiles and the SP properties of the non-UV upturn galaxies in our sample are comparable to those of the UV upturn galaxies. This similarity may arise from the presence of residual star formation in the non-UV upturn systems.

Li, Xiejin [Chinese Academy of Sciences; Universit↗

Learning and Predicting Photonic Responses of Plasmonic Nanoparticle Assemblies via Dual Variational Autoencoders

In this work, the application of machine learning is demonstrated for rapid and accurate extraction of plasmonic particles cluster geometries from hyperspectral image data via a dual variational autoencoder (dual-VAE). In this approach, the information is shared between the latent spaces of two VAEs acting on the particle shape data and spectral data, respectively, but enforcing a common encoding on the shape-spectra pairs. It is shown that this approach can establish the relationship between the geometric characteristics of nanoparticles and their far-field photonic responses, demonstrating that hyperspectral darkfield microscopy can be used to accurately predict the geometry (number of particles, arrangement) of a multiparticle assemblies below the diffraction limit in an automated fashion with high fidelity (for monomers (0.96), dimers (0.86), and trimers (0.58). This approach of building structure-property relationships via shared encoding is universal and should have applications to a broader range of materials science and physics problems in imaging of both molecular and nanomaterial systems.

variational autoencoder↗

Giant Wilson loops and AdS 2 /dCFT 1

The 1/2-BPS Wilson loop in N = 4 supersymmetric Yang-Mills theory is an important and well-studied example of conformal defect. In particular, much work has been done for the correlation functions of operator insertions on the Wilson loop in the fundamental representation. In this paper, we extend such analyses to Wilson loops in the large-rank symmetric and antisymmetric representations, which correspond to probe D3 and D5 branes with AdS 2 × S 2 and AdS 2 × S 4 worldvolume geometries, ending at the AdS 5 boundary along a one-dimensional contour. We first compute the correlation functions of protected scalar insertions from supersymmetric localization, and obtain a representation in terms of multiple integrals that are similar to the eigenvalue integrals of the random matrix, but with important differences. Using ideas from the Fermi Gas formalism and the Clustering method, we evaluate their large N limit exactly as a function of the ’t Hooft coupling. The results are given by simple integrals of polynomials that resemble the Q-functions of the Quantum Spectral Curve, with integration measures depending on the number of insertions. Next, we study the correlation functions of fluctuations on the probe D3 and D5 branes in AdS. We compute a selection of three- and four-point functions from perturbation theory on the D-branes, and show that they agree with the results of localization when restricted to supersymmetric kinematics. We also explain how the difference of the internal geometries of the D3 and D5 branes manifests itself in the localization computation.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

2p x-ray absorption spectroscopy of 3d transition metal systems

This review provides an overview of the different methods and computer codes that are used to interpret 2p x-ray absorption spectra of 3d transition metal ions. We first introduce the basic parameters and give an overview of the methods used. We start with the semi-empirical multiplet codes and compare the different codes that are available. A special chapter is devoted to the user friendly interfaces that have been written on the basis of these codes. Next we discuss the first principle codes based on band structure, including a chapter on Density Functional theory based approaches. We also give an overview of the first-principle multiplet codes that start from a cluster calculation and we discuss the wavefunction based methods, including multi-reference methods. We end the review with a discussion of the link between theory and experiment and discuss the open issues in the spectral analysis.

36 MATERIALS SCIENCE↗

The gas-phase mass–metallicity relation of dwarf galaxies across large-scale environments using the CAVITY parent sample

Context. The gas-phase mass–metallicity relation (MZR) of galaxies shows a noticeable break in slope and an increased scatter at low stellar masses, suggesting that the physical processes governing chemical enrichment differ between dwarf and high-mass systems. Dwarf galaxies, in particular, are highly susceptible to both internal and environmental mechanisms due to their shallow potential wells. Aims. The primary aim of this work is to assess whether a single, universal MZR can describe dwarf galaxies across diverse large-scale environments, or whether systematic environmental variations emerge. To probe these, we examine the MZR and star formation rate (SFR) of dwarf galaxies with stellar masses in the range of 8.9 < log(M ★ /M ⊙ ) < 9.5. Methods. Using optical spectra from the Sloan Digital Sky Survey, we measured the fluxes of key emission lines via the pyPipe3D full spectral fitting pipeline. Aperture-corrected fluxes, along with multiple metallicity indicators and calibrations, were used to derive the MZR and the SFR for 353, 311, and 22 dwarf galaxies located in voids, filaments, and clusters, respectively. Results. We find a systematic variation in the MZR slope, steeper in voids (0.28 ± 0.03) and progressively flatter in clusters (0.17 ± 0.08), indicating a dependence of the MZR on the large-scale environment in this mass regime. When galaxies are separated by local density, no significant differences are observed between isolated and non-isolated dwarfs in voids. Isolated dwarf galaxies in filaments also exhibit properties similar to those of their counterparts in voids. However, non-isolated filament galaxies exhibit similar MZR slopes comparable to those of cluster dwarfs and flatter slopes than their counterparts in voids. Conclusions. We report both large- and local-scale environmental dependencies in the gas-phase metallicity and in the slope of the MZR for dwarf galaxies. Consistent with the general consensus on the pre-processing of galaxies in filaments, our results indicate that the influence of the local environment becomes increasingly significant within the filamentary regions of the cosmic web, affecting the chemical enrichment and star formation activity of low-mass systems. These findings further suggest that a portion of the scatter commonly observed in the MZR of dwarf galaxies arises from environmental effects.

Bidaran, Bahar [Dpto. de Física Teórica y del Cosm↗

Abundances of Neutron-capture Elements in 62 Stars in the Globular Cluster Messier 15

M15 is a globular cluster with a known spread in neutron-capture elements. This paper presents abundances of neutron-capture elements for 62 stars in M15. Spectra were obtained with the Michigan/Magellan Fiber System spectrograph, covering a wavelength range from ~4430 to 4630 Å. Spectral lines from Fe I , Fe II , Sr I , Zr II , Ba II , La II , Ce II , Nd II , Sm II , Eu II , and Dy II were measured, enabling classifications and neutron-capture abundance patterns for the stars. Of the 62 targets, 44 are found to be highly Eu-enhanced r-II stars, another 17 are moderately Eu-enhanced r-I stars, and one star is found to have an s-process signature. The neutron-capture patterns indicate that the majority of the stars are consistent with enrichment by the r-process. The 62 target stars are found to show significant star-to-star spreads in Sr, Zr, Ba, La, Ce, Nd, Sm, Eu, and Dy, but no significant spread in Fe. The neutron-capture abundances are further found to have slight correlations with sodium abundances from the literature, unlike what has been previously found; follow-up studies are needed to verify this result. The findings in this paper suggest that the Eu-enhanced stars in M15 were enhanced by the same process, that the nucleosynthetic source of this Eu pollution was the r-process, and that the r-process source occurred as the first generation of cluster stars was forming.

79 ASTRONOMY AND ASTROPHYSICS↗

Emergence of quasiparticles in a doped Mott insulator

How a Mott insulator develops into a weakly coupled metal upon doping is a central question to understanding various emergent correlated phenomena. To analyze this evolution and its connection to the high- T c cuprates, we study the single-particle spectrum for the doped Hubbard model using cluster perturbation theory on superclusters. Starting from extremely low doping, we identify a heavily renormalized quasiparticle dispersion that immediately develops across the Fermi level, and a weakening polaronic side band at higher binding energy. The quasiparticle spectral weight roughly grows at twice the rate of doping in the low doping regime, but this rate is halved at optimal doping. In the heavily doped regime, we find both strong electron-hole asymmetry and a persistent presence of Mott spectral features. Finally, we discuss the applicability of the single-band Hubbard model to describe the evolution of nodal spectra measured by angle-resolved photoemission spectroscopy (ARPES) on the single-layer cuprate La 2– x Sr x CuO 4 (0 ≤ x ≤ 0.15). This work benchmarks the predictive power of the Hubbard model for electronic properties of high- T c cuprates.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

New Subgrouping of Multiple Stellar Populations in NGC 2808 Based on Low-resolution Spectroscopy

We performed low-resolution spectroscopy for the red giant branch stars in an intriguing globular cluster (GC) NGC 2808, which hosts subpopulations with extreme helium and light-element abundances. In order to trace N, C, and Ca abundance differences among subpopulations, we measured CN, CH, and Ca ii H&K spectral indices, respectively. We identified four subpopulations (G1, G2, G3, and G4) from CN and CH strength, with CN-weak/CH-strong G1, CN-intermediate/CH-strong G2, CN-strong/CH-intermediate G3, and CN-strong/CH-weak G4. Compared to [Na/O] from high-resolution spectroscopy, we show that CN index can more clearly separate G1 and G2. Since CN traces N abundance in a GC, it implies that G1 and G2 would show a larger difference in [N/Fe] compared to [Na/Fe], as predicted by chemical evolution models. Later generation stars G3 and G4, however, are better separated with high-resolution spectroscopy. We also found that G4 shows a stronger Ca ii H&K line strength compared to that of G1, but we suspect this to be a result of unusually strong He enhancement and/or Mg depletion in G4 of this GC. This work illustrates that combining low- and high-resolution spectroscopic studies can improve the separation of subpopulations in GCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic structure and photophysics of a supermolecular iron complex having a long MLCT-state lifetime and panchromatic absorption

Exploiting earth-abundant iron-based metal complexes as high-performance photosensitizers demands long-lived electronically excited metal-to-ligand charge-transfer (MLCT) states, but these species suffer typically from femtosecond timescale charge-transfer (CT)-state quenching by low-lying nonreactive metal-centered (MC) states. Here, we engineer supermolecular Fe(II) chromophores based on the bis(tridentate-ligand)metal(II)-ethyne-(porphinato)zinc(II) conjugated framework, previously shown to give rise to highly delocalized low-lying 3 MLCT states for other Group VIII metal (Ru, Os) complexes. Electronic spectral, potentiometric, and ultrafast pump–probe transient dynamical data demonstrate that a combination of a strong σ-donating tridentate ligand and a (porphinato)zinc(II) moiety with low-lying π*-energy levels, sufficiently destabilize MC states and stabilize supermolecular MLCT states to realize Fe(II) complexes that express 3 MLCT state photophysics reminiscent of their heavy-metal analogs. The resulting Fe(II) chromophore archetype, FeNHCPZn, features a highly polarized CT state having a profoundly extended 3MLCT lifetime (160 ps), 3 MLCT phosphorescence, and ambient environment stability. Density functional and domain-based local pair natural orbital coupled cluster [DLPNO-CCSD(T)] theory reveal triplet-state wavefunction spatial distributions consistent with electronic spectroscopic and excited-state dynamical data, further underscoring the dramatic Fe metal-to-extended ligand CT character of electronically excited FeNHCPZn. This design further prompts intense panchromatic absorptivity via redistributing high-energy absorptive oscillator strength throughout the visible spectral domain, while maintaining a substantial excited-state oxidation potential for wide-ranging photochemistry––highlighted by the ability of FeNHCPZn to photoinject charges into a SnO 2 /FTO electrode in a dye-sensitized solar cell (DSSC) architecture. Concepts enumerated herein afford opportunities for replacing traditional rare-metal–based emitters for solar-energy conversion and photoluminescence applications.

74 ATOMIC AND MOLECULAR PHYSICS↗

Quantum dynamics in strongly driven random dipolar magnets

The random dipolar magnet LiHo x Y 1– x F 4 enters a strongly frustrated regime for small Ho 3+ concentrations with x < 0.05. In this regime, the magnetic moments of the Ho 3+ ions experience small quantum corrections to the common Ising approximation of LiHo x Y 1– x F 4 , which lead to a $\mathbb{Z}_2$-symmetry breaking and small, degeneracy breaking energy shifts between different eigenstates. Here we show that destructive interference between two almost degenerate excitation pathways burns spectral holes in the magnetic susceptibility of strongly driven magnetic moments in LiHo x Y 1– x F 4 . Such spectral holes in the susceptibility, microscopically described in terms of Fano resonances, can already occur in setups of only two or three frustrated moments, for which the driven level scheme has the paradigmatic Λ shape. For larger clusters of magnetic moments, the corresponding level schemes separate into almost isolated many-body Λ schemes, in the sense that either the transition matrix elements between them are negligibly small or the energy difference of the transitions is strongly off-resonant to the drive. This enables the observation of Fano resonances, caused by many-body quantum corrections to the common Ising approximation also in the thermodynamic limit. Finally, we discuss its dependence on the driving strength and frequency as well as the crucial role that is played by lattice dissipation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantum Filtering and Analysis of Multiplicities in Eigenvalue Spectra

Fine-grained spectral properties of quantum Hamiltonians, including both eigenvalues and their multiplicities, provide useful information for characterizing many-body quantum systems as well as for understanding phenomena such as topological order. Extracting such information with small additive error is #BQP-complete in the worst case. In this work, we introduce QFAMES (quantum filtering and analysis of multiplicities in eigenvalue spectra), a quantum algorithm that efficiently identifies clusters of closely spaced dominant eigenvalues and determines their multiplicities under physically motivated assumptions, which allows us to bypass worst-case complexity barriers. QFAMES also enables the estimation of observable expectation values within targeted energy clusters, providing a powerful tool for studying quantum phase transitions and other physical properties. We validate the effectiveness of QFAMES through numerical demonstrations, including its applications to characterizing quantum phases in the transverse-field Ising model and estimating the ground-state degeneracy of a topologically ordered phase in the two-dimensional toric code model. We also generalize QFAMES to the setting of mixed initial states. Our approach offers rigorous theoretical guarantees and significant advantages over existing subspace-based quantum spectral analysis methods, particularly in terms of the sample complexity and the ability to resolve degeneracies.

97 MATHEMATICS AND COMPUTING↗

eROSITA study of the globular cluster 47 Tucanae

Here, we present the results of the analysis of five observations of the globular clutser 47 Tucanae (47 Tuc) with the extended Roentgen Survey with an Imaging Telescope Array (eROSITA) on board the Spektrum-Roentgen-Gamma (Spektr-RG, SRG). We study the X-ray population in the field of one of the most massive globular clusters in our Milky Way. We focused on the classification of point-like sources in the field of 47 Tuc. The unresolved dense core of 47 Tuc (1.7 radius) and also sources that show extended emission are excluded from this study. We applied different methods of X-ray spectral and timing analysis together with multi-wavelength studies to classify the X-rays sources in the field of 47 Tuc. We detected 888 point-like sources in the energy range of 0.2–5.0 keV. We identified 126 background active galactic nuclei and 25 foreground stars. One of the foreground stars is classified as a variable M dwarf. We also classified 14 X-ray sources as members of 47 Tuc, including one symbiotic star, two quiescent low-mass X-ray binaries, and four cataclysmic variables. There are also five X-ray sources that can either be a cataclysmic variable or a contact binary, and also one X-ray source can be an active binary (type RS CVn). We identified one X-ray binary that belongs to the Small Magellanic Cloud. Moreover, we calculated the X-ray luminosity function of 47 Tuc. No significant population that seems to belong to the globular cluster is observed in the energy range of 0.5–2.0 keV using eROSITA observations.

79 ASTRONOMY AND ASTROPHYSICS↗

Molecular Examination of Ion-Pair Competition in Alkaline Aluminate Solutions Using In Situ Liquid SIMS

Understanding the structure and composition of aluminate complexes in extremely alkaline systems such as Bayer liquors has received enormous attentions due to its fundamental and industrial importance. However, obtaining direct molecular information of the underlying ion-ion interactions using traditional approaches such as NMR or Raman spectroscopy is challenging due to the weakness of these interactions and/or their complex overlapping spectral signatures. Here, we exploit in situ liquid secondary ion mass spectrometry (SIMS) as a new approach and show how it enables new insights. In contrast with traditional techniques, using SIMS we succeeded in acquiring information on dominant ion clusters in these alkaline systems. In Na + /K + mixed alkaline aluminate solutions we clearly observe preferential formation of Na + -anion clusters over K + -anion clusters. Further, evaluation of these clusters by density functional theory (DFT) calculations shows that these structures are stable and that their relative bond energies are consistent with their observed SIMS signal intensity differences. This demonstrates a key advantage of in situ liquid SIMS for overcoming ambiguities obscuring important information in these systems on constituent molecular clusters defined by relatively weak ion pair competition and ion-solvent interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

HypoRiPPAtlas as an Atlas of hypothetical natural products for mass spectrometry database search

Abstract Recent analyses of public microbial genomes have found over a million biosynthetic gene clusters, the natural products of the majority of which remain unknown. Additionally, GNPS harbors billions of mass spectra of natural products without known structures and biosynthetic genes. We bridge the gap between large-scale genome mining and mass spectral datasets for natural product discovery by developing HypoRiPPAtlas, an Atlas of hypothetical natural product structures, which is ready-to-use for in silico database search of tandem mass spectra. HypoRiPPAtlas is constructed by mining genomes using seq2ripp, a machine-learning tool for the prediction of ribosomally synthesized and post-translationally modified peptides (RiPPs). In HypoRiPPAtlas, we identify RiPPs in microbes and plants. HypoRiPPAtlas could be extended to other natural product classes in the future by implementing corresponding biosynthetic logic. This study paves the way for large-scale explorations of biosynthetic pathways and chemical structures of microbial and plant RiPP classes.

60 APPLIED LIFE SCIENCES↗

Asynchronous x-ray multiprobe data acquisition for x-ray transient absorption spectroscopy

Laser pump X-ray Transient Absorption (XTA) spectroscopy offers unique insights into photochemical and photophysical phenomena. X-ray Multiprobe data acquisition (XMP DAQ) is a technique that acquires XTA spectra at thousands of pump-probe time delays in a single measurement, producing highly self-consistent XTA spectral dynamics. In this work, we report two new XTA data acquisition techniques that leverage the high performance of XMP DAQ in combination with High Repetition Rate (HRR) laser excitation: HRR-XMP and Asynchronous X-ray Multiprobe (AXMP). HRR-XMP uses a laser repetition rate up to 200 times higher than previous implementations of XMP DAQ and proportionally increases the data collection efficiency at each time delay. This allows HRR-XMP to acquire more high-quality XTA data in less time. AXMP uses a frequency mismatch between the laser and x-ray pulses to acquire XTA data at a flexibly defined set of pump-probe time delays with a spacing down to a few picoseconds. AXMP introduces a novel pump-probe synchronization concept that acquires data in clusters of time delays. Further, the temporally inhomogeneous distribution of acquired data improves the attainable signal statistics at early times, making the AXMP synchronization concept useful for measuring sub-nanosecond dynamics with photon-starved techniques like XTA. In this paper, we demonstrate HRR-XMP and AXMP by measuring the laser-induced spectral dynamics of dilute aqueous solutions of Fe(CN) 6 4₋ and [Fe II (bpy) 3 ] 2+ (bpy: 2,2'-bipyridine), respectively.

47 OTHER INSTRUMENTATION↗

Excited-State Dynamics during Primary C–I Homolysis in Acetyl Iodide Revealed by Ultrafast Core-Level Spectroscopy

In typical carbonyl-containing molecules, bond dissociation events follow initial excitation to $nπ_{C=O}$$^*$ states. However, in acetyl iodide, the iodine atom gives rise to electronic states with mixed $nπ_{C=O}$$^*$ and $nπ_{C–I}$$^*$ character, leading to complex excited-state dynamics, ultimately resulting in dissociation. Using ultrafast extreme ultraviolet (XUV) transient absorption spectroscopy and quantum chemical calculations, we present an investigation of the primary photodissociation dynamics of acetyl iodide via time-resolved spectroscopy of core-to-valence transitions of the I atom after 266 nm excitation. The probed I 4d-to-valence transitions show features that evolve on sub-100-fs time scales, reporting on excited-state wavepacket evolution during dissociation. These features subsequently evolve to yield spectral signatures corresponding to free iodine atoms in their spin–orbit ground and excited states with a branching ratio of 1.1:1 following dissociation of the C–I bond. Calculations of the valence excitation spectrum via equation-of-motion coupled cluster with single and double substitutions (EOM-CCSD) show that initial excited states are of spin-mixed character. From the initially pumped spin-mixed state, we use a combination of time-dependent density functional theory (TDDFT)-driven nonadiabatic ab initio molecular dynamics and EOM-CCSD calculations of the N$_{4,5}$ edge to reveal a sharp inflection point in the transient XUV signal that corresponds to rapid C–I homolysis. Here, by examining the molecular orbitals involved in the core-level excitations at and around this inflection point, we are able to piece together a detailed picture of C–I bond photolysis in which d → σ* transitions give way to d → p excitations as the bond dissociates. We also report theoretical predictions of short-lived, weak 4d → 5d transitions in acetyl iodide, validated by weak bleaching in the experimental transient XUV spectra. This joint experimental–theoretical effort has thus unraveled the detailed electronic structure and dynamics of a strongly spin–orbit coupled system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗