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At least 289 records · Page 16

Diagnostics of Carbon Nanotube Formation in a Laser Produced Plume: An Investigation of the Metal Catalyst by Laser Ablation Atomic Fluorescence Spectroscopy

Carbon nanotubes, elongated molecular tubes with diameters of nanometers and lengths in microns, hold great promise for material science. Hopes for super strong light-weight material to be used in spacecraft design is the driving force behind nanotube work at JSC. The molecular nature of these materials requires the appropriate tools for investigation of their structure, properties, and formation. The mechanism of nanotube formation is of particular interest because it may hold keys to controlling the formation of different types of nanotubes and allow them to be produced in much greater quantities at less cost than is currently available. This summer's work involved the interpretation of data taken last summer and analyzed over the academic year. The work involved diagnostic studies of carbon nanotube formation processes occurring in a laser-produced plume. Laser ablation of metal doped graphite to produce a plasma plume in which carbon nanotubes self assemble is one method of making carbon nanotube. The laser ablation method is amenable to applying the techniques of laser spectroscopy, a powerful tool for probing the energies and dynamics of atomic and molecular species. The experimental work performed last summer involved probing one of the metal catalysts, nickel, by laser induced fluorescence. The nickel atom was studied as a function of oven temperature, probe laser wavelength, time after ablation, and position in the laser produced plume. This data along with previously obtained data on carbon was analyzed over the academic year. Interpretations of the data were developed this summer along with discussions of future work. The temperature of the oven in which the target is ablated greatly influences the amount of material ablated and the propagation of the plume. The ablation conditions and the time scale of atomic and molecular lifetimes suggest that initial ablation of the metal doped carbon target results in atomic and small molecular species. The metal atoms survive for several milliseconds while the gaseous carbon atoms and small molecules nucleate more rapidly. Additional experiments and the development of in situ methods for carbon nanotube detection would allow these results to be interpreted from the perspective of carbon nanotube formation.

deBoer, Gary↗

Mechanistic Investigation of Molybdenum Disulfide Defect Photoluminescence Quenching by Adsorbed Metallophthalocyanines

Lattice defects play an important role in determining the optical and electrical properties of monolayer semiconductors such as MoS 2 . Although the structures of various defects in monolayer MoS 2 are well studied, little is known about the nature of the fluorescent defect species and their interaction with molecular adsorbates. In this study, the quenching of the low-temperature defect photoluminescence (PL) in MoS 2 is investigated following the deposition of metallophthalocyanines (MPcs). The quenching is found to significantly depend on the identity of the phthalocyanine metal, with the quenching efficiency decreasing in the order CoPc > CuPc > ZnPc, and almost no quenching by metal-free H 2 Pc is observed. Futher, time-correlated single photon counting (TCSPC) measurements corroborate the observed trend, indicating a decrease in the defect PL lifetime upon MPc adsorption, and the gate voltage-dependent PL reveals the suppression of the defect emission even at large Fermi level shifts. Density functional theory modeling argues that the MPc complexes stabilize dark negatively charged defects over luminescent neutral defects through an electrostatic local gating effect. These results demonstrate the control of defectbased excited-state decay pathways via molecular electronic structure tuning, which has broad implications for the design of mixeddimensional optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fluorescence Studies of Protein Crystal Nucleation

One of the most powerful and versatile methods for studying molecules in solution is fluorescence. Crystallization typically takes place in a concentrated solution environment, whereas fluorescence typically has an upper concentration limit of approximately 1 x 10(exp -5)M, thus intrinsic fluorescence cannot be employed, but a fluorescent probe must be added to a sub population of the molecules. However the fluorescent species cannot interfere with the self-assembly process. This can be achieved with macromolecules, where fluorescent probes can be covalently attached to a sub population of molecules that are subsequently used to track the system as a whole. We are using fluorescence resonance energy transfer (FRET) to study the initial solution phase self-assembly process of tetragonal lysozyme crystal nucleation, using covalent fluorescent derivatives which crystallize in the characteristic P432121 space group. FRET studies are being carried out between cascade blue (CB-lys, donor, Ex 376 nm, Em 420 nm) and lucifer yellow (LY-lys, acceptor, Ex 425 nm, Em 520 nm) asp101 derivatives. The estimated R0 for this probe pair, the distance where 50% of the donor energy is transferred to the acceptor, is approximately 1.2 nm, compared to 2.2 nm between the side chain carboxyls of adjacent asp101's in the crystalline 43 helix. The short CB-lys lifetime (approximately 5 ns), coupled with the large average distances between the molecules ((sup 3) 50 nm) in solution, ensure that any energy transfer observed is not due to random diffusive interactions. Addition of LY-lys to CB-lys results in the appearance of a second, shorter lifetime (approximately 0.2 ns). Results from these and other ongoing studies will be discussed in conjunction with a model for how tetragonal lysozyme crystals nucleate and grow, and the relevance of that model to microgravity protein crystal growth

Pusey, Marc L.↗

The properties of the nitrogen-vacancy center in milled chemical vapor deposition nanodiamonds

Fluorescent nanodiamonds (FNDs) containing negatively charged nitrogen-vacancy (NV − ) centers are vital for many emerging quantum sensing applications from magnetometry to intracellular sensing in biology. However, developing a scalable fabrication method for FNDs hosting color centers with consistent bulk-like photoluminescence (PL) and spin coherence properties remains a highly desired but unrealized goal. Here, we investigate optimized ball milling of single-crystal diamonds produced via chemical vapor deposition (CVD) and containing 2 ppm of substitutional nitrogen and 0.3 ppm of NV − to achieve this goal. The NV charge state, PL lifetime, and spin properties of bulk CVD diamond samples are directly compared to milled CVD FNDs and commercial high-pressure high-temperature (HPHT) FNDs. We find that on average, the relative contribution of the NV − charge state to the total NV PL is lower and the NV PL lifetime is longer in CVD FNDs compared to HPHT FNDs, both likely due to the lower N s 0 concentration in CVD FNDs. The CVD bulk and CVD FNDs on average show similar average T 1 spin relaxation times of 3.2 ± 0.7 ms and 4.7 ± 1.6 ms, respectively, compared to 0.17 ± 0.01 ms for commercial HPHT FNDs. Our results demonstrate that ball milling of CVD diamonds enables the large-scale fabrication of NV ensembles in FNDs with bulk-like T 1 spin relaxation properties.

chemical vapor deposition↗

Ba +2 ion trapping using organic submonolayer for ultra-low background neutrinoless double beta detector

If neutrinos are their own antiparticles the otherwise-forbidden nuclear reaction known as neutrinoless double beta decay can occur. The very long lifetime expected for these exceptional events makes its detection a daunting task. In order to conduct an almost background-free experiment, the NEXT collaboration is investigating novel synthetic molecular sensors that may capture the Ba dication produced in the decay of certain Xe isotopes in a high-pressure gas experiment. The use of such molecular detectors immobilized on surfaces must be explored in the ultra-dry environment of a xenon gas chamber. Here, using a combination of highly sensitive surface science techniques in ultra-high vacuum, we demonstrate the possibility of employing the so-called Fluorescent Bicolor Indicator as the molecular component of the sensor. We unravel the ion capture process for these molecular indicators immobilized on a surface and explain the origin of the emission fluorescence shift associated to the ion trapping.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Hydrogel-Immobilized Multienzyme Systems for Cell-Free Chemical Bioproduction

Cell-free gene expression systems derived from bacterial lysates enable the expression of biosynthetic pathways from inexpensive and easily prepared DNA templates. These systems hold great promise for modular and on-demand bioproduction of valuable small molecules in resource-limited settings but are constrained in their long-term stability, reusability, and deployability. In this work, we demonstrate that multiple cell-free expressed enzymes can be co-immobilized in biocompatible hydrogels made from poly(ethylene glycol) diacrylate (PEGDA) with added glycerol for enhanced gel integrity. Using small-angle X-ray scattering (SAXS), we show that the mesh size of PEGDA-glycerol hydrogels is comparable to the globular sizes of many proteins and enzymes, which could be used for protein entrapment. We found that the combination between entrapment and chemical ligation of the enzymes was effective to retain proteins. By employing a method for direct fluorescence measurement from hydrogels, we found that proteins can be retained in PEGDA-glycerol for at least a week. By separating the cell-free enzyme expression from the immobilization step, we successfully fabricated enzyme-laden hydrogels with three heterologous cell-free enzymes for the bioconversion of pyruvic acid to malic acid, an industrially valuable and versatile precursor chemical. Both heterologous and endogenous enzymes from the lysate remain functional in photo-cross-linked hydrogels and can be reused for multiple biocatalytic cycles. Moreover, we also found that the immobilized enzymes exhibit up to 1.6-fold higher activity and 2-fold longer lifetimes than free enzymes in liquid reactions. Furthermore, these results could advance the deployment of cell-free synthetic biology because they show that reusable, stable, and durable multienzyme systems can be created using readily available materials and fabrication techniques.

59 BASIC BIOLOGICAL SCIENCES↗

Xenon lighting adjusted to plant requirements

Xenon lamps are available as low and high power lamps with relatively high efficiency and a relatively long lifetime up to several thousand hours. Different construction types of short-arc and long-arc lamps permit a good adaptation to various applications in projection and illumination techniques without substantial changes of the spectral quality. Hence, the xenon lamp was the best choice for professional technical purposes where high power at simultaneously good spectral quality of the light was required. However, technical development does not stand still. Between the luminous efficacy of xenon lamps of 25-50 lm/W and the theoretical limit for 'white light' of 250 lm/W is still much room for improvement. The present development mainly favors other lamp types, like metal halide lamps and fluorescent lamps for commercial lighting purposes. The enclosed sections deal with some of the properties of xenon lamps relevant to plant illumination; particularly the spectral aspects, the temporal characteristics of the emission, and finally the economy of xenon lamps will be addressed. Due to radiation exceeding the natural global radiation in both the ultraviolet (UV) and the infrared (IR) regions, filter techniques have to be included into the discussion referring to the requirements of plant illumination. Most of the presented results were obtained by investigations in the GSF phytotron or in the closed Phytocell chambers of the University of Erlangen. As our experiences are restricted to area plant illumination rather than spot lights our discussion will concentrate on low pressure long-arc xenon lamps which are commonly used for such plant illuminations. As the spectral properties of short-arc lamps do not differ much from those of long-arc lamps most of our conclusions will be valid for high pressure xenon lamps too. These lamps often serve as light sources for small sun simulators and for monochromators which are used for action spectroscopy of plant responses.

Koefferlein, M.↗

Athermal phonon collection efficiency in diamond crystals for low mass dark matter detection

Here, we explored the efficacy of lab-grown diamonds as potential target materials for the direct detection of sub-GeV dark matter (DM) using metallic magnetic calorimeters (MMCs). Diamond, with its excellent phononic properties and the low atomic mass of the constituent carbon, can play a crucial role in detecting low mass dark matter particles. The relatively long electron-hole pair lifetime inside the crystal may provide discrimination power between the DM-induced nuclear recoil events and the background-induced electron recoil events. Utilizing the fast response times of the MMCs and their unique geometric versatility, we deployed a novel methodology for quantifying phonon dynamics inside diamond crystals. We demonstrated that lab-grown diamond crystals fabricated via the chemical vapor deposition (CVD) technique can satisfy the stringent quality requirements for sub-GeV dark matter searches. The high-quality polycrystalline CVD diamond showed a superior athermal phonon collection efficiency compared to that of the reference sapphire crystal, and achieved energy resolution 62.7 eV at the 8.05 keV copper fluorescence line. With this energy resolution, we explored the low-energy range below 100 eV and confirmed the existence of so-called low-energy excess (LEE) reported by multiple cryogenic experiments.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Rotationally resolved collisional transfer rates in OH

Fluorescence lidar measurements of the hydroxyl radical require detailed information concerning collision induced processes in order to deduce the radical number density from a lidar return. The Goddard SFC OH lidar currently utilizes a broadband detector which precludes the necessity of fully understanding collisional redistribution of rotational energy within the excited state. Numerous advantages result however from the inclusion of a detector with a bandpass only slightly larger that the Doppler width of a rotational line. This however places more stringent requirements on the spectroscopy. Measurements were accordingly made of rotationally resolved quenching rates for collisions with O2, N2, and H2O. Rotational transfer rates were also measured for the same colliders. Quenching rates were measured using a Nd-YAG pumped Rh6G dye laser doubled into the UV. The OH lifetimes were measured as a function of pressure of quenching gas at total pressures of between 50 and 250 microns. Rotational transfer rates were measured by recording the emission spectrum on an intensified diode array and integrating over 10.000 laser shots.

Mcgee, T. J.↗

Pulse Radiolysis Investigation of Radicals Derived from Water-Soluble Cyanine Dyes: Implications for Super-resolution Microscopy

Light-induced blinking, an inherent feature of many forms of super-resolution microscopy, has been linked to transient reduction of the fluorescent cyanine dye used as an imaging agent. There is, however, only scant literature information related to one-electron reduced cyanine dyes, especially in an aqueous environment. Here, we examine a small series of cyanine dyes, possessing disparate π-conjugation lengths, under selective reducing or oxidizing conditions. The experiment allows recording of both differential absorption spectra and decay kinetics of the resultant one-electron reduced or oxidized transient species in water. Relative to the ground state, absorption transitions for the various radicals are weak and somewhat broadened but do allow correlation with the π-conjugation length. In all cases, absorption maxima lie to the blue of the main ground-state transition. Under anaerobic conditions, the transient species decay on the microsecond to millisecond time scale, with the mean lifetime depending on molecular structure, radiation dose, and dye concentration. The experimental absorption spectra recorded for the one-electron reduced radicals and the presumed dimer cation radical compare well to spectra obtained from time-dependent density functional theory calculations. Furthermore, the results allow conclusions to be drawn regarding the plausibility of the reduced species being responsible for light-induced blinking in direct stochastic optical reconstruction microscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance and lifetime of intercalative water deionization cells for mono- and divalent ion removal

We report intercalative deionization (IDI) uses two cation intercalation electrodes separated by an anion exchange membrane in a symmetric cell design that has the potential to deliver electrochemically desalinated water in an energy- and water-efficient way. Here, we define and measure metrics to describe the performance and lifetime of IDI cells and compare them for NaCl and CaCl 2 feed solutions. With 20 mM NaCl, NiHCF/AEM/NiHCF flow cells achieve 10 mM average concentration change at a productivity of 20 l/h/m 2 and 5 mM average concentration change at 130 l/h/m 2 . In both cases the cells are operated at a 3C current rate and consume ~30 Wh/m 3 of energy. With 10 mM CaCl 2 , the specific capacity and salt removal of IDI flow cells is ~4 times lower. NiHCF/NiHCF beaker cells with CaCl 2 electrolyte suffer from strong capacity fade, while the same cells with NaCl electrolyte achieve 500 cycles without any capacity fade. Our post-mortem analysis using X-ray diffraction, secondary electron microscopy, energy dispersive X-ray spectroscopy, synchrotron-based X-ray absorption spectroscopy and micro X-ray fluorescence mapping reveals that NiHCF dissolves upon repeated intercalation with Ca 2+ , releasing residual K + , Ni 2+ and Fe(CN) 6 3 , which precipitates as a crystalline decomposition product on the electrodes. This side reaction deprives the active material NiHCF of charge compensating Fe, and thus accounts for the observed capacity fade.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrasonication-assisted trace amount solvent synthesis of Cs 4 PbBr 6 crystal with ultra-bright green light emission

Cs 4 PbBr 6 crystals have been synthesized by an ultrasonication-assisted trace amount polar solvent method. The prepared green Cs 4 PbBr 6 material was found to have high photoluminescence (PL) brightness and 10 ns PL lifetime. The prepared green light emitting device can achieve the maximum brightness of 3.8 × 10 9 cd/m 2 , which is nearly 100 times higher than a wick. The white light emitting device based on Cs 4 PbBr 6 crystals has better performance than commercial products, which can cover 32.3% of the color gamut and achieves 107.3% coverage for International Commission on Illumination (CIE)1931 and 84.8% coverage for CIE1976.

36 MATERIALS SCIENCE↗

Photophysical Properties and Electronic Structure of Hydroporphyrin Dyads Exhibiting Strong Through-Space and Through-Bond Electronic Interactions

Electronic interactions between tetrapyrroles are utilized in natural photosynthetic systems to tune the light-harvesting and energy/charge-transfer processes in these assemblies. Such interactions also can be employed to tailor the electronic properties of tetrapyrrolic dyads and larger arrays for use in materials science and biomedical research. Here we have utilized static and time-resolved optical spectroscopy to characterize the optical absorption and emission properties of a set of chlorin and bacteriochlorin dyads with varied degrees of through-bond (TB) and through-space (TS) interactions between the constituent macrocycles. The dyads consist of two chlorins or two bacteriochlorins joined by a linker that utilizes a triple-double-triple bond (enediyne) motif in which the double bond portion is a ester-substituted ethylene or o-phenylene unit. The photophysical studies are coupled with density functional theory (DFT) calculations to probe the ground-state molecular orbital (MO) characteristics of the dyads and time-dependent calculations (TDDFT) to elucidate excited-state properties. The latter include electronic characteristics of the singlet excited state manifold and the absorption transitions to these states from the electronic ground state. Comparison of the MO and calculated spectral properties of each dyad with the linker present versus disrupted (by eliminating the double-bond portion) gives insight into the relative contributions of TB versus TS interactions to the electronic properties of the dyads. The results show that the TB and TS contributions are additive (constructively interfere), which is not always the case for molecular dyads. Most of the dyads have shorter lifetimes of the lowest singlet excited state compared to the parent monomer, which derives from increased S 1 → S 0 internal conversion. The enhancement is greater for the dyads in benzonitrile than in toluene. Furthermore, the studies provide insights into the nature of the electronic interactions between the constituents in the tetrapyrrole arrays and how these interactions dictate the spectral properties and excited-state decay characteristics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photophysics and Spin-Physics Studies on Persistent Upconversion Luminescence from Nonlinearly Polarizable Ferroelectric-Like Lattice Prepared by Orderly Packing Donor–Acceptor Structures under Multiphoton Excitation

The ultralong-lived upconversion luminescence with the lifetime of 0.48 s in a broad spectral range (530–650 nm) is observed in CD49 (9-(3-(5-bromopyridin-3-yl)prop-2-yn-1-yl)-9H-carbazole) crystal designed with donor–acceptor (carbazole–pyridine) structures under infrared excitation, simultaneously accompanied with second harmonic generation (SHG). This phenomenon indicates orderly packing donor–acceptor structures form a nonlinearly polarizable ferroelectric-like lattice with ultralong-lived light-emitting states, leading to much prolonged nonlinear optical behaviors. The persistent upconversion luminescence together with SHG is largely reduced when lowering crystallinity. This implies that nonlinearly polarizable ferroelectric-like lattice provides the necessary condition to generate persistent upconversion luminescence. Evidently, persistent upconversion luminescence becomes completely lacking when only using ultralong-lived light-emitting states without nonlinearly polarizable ferroelectric-like lattice, exampled by 4-(dimethylamino)benzonitrile dispersed in polyvinyl alcohol matrix. Magneto-photoluminescence shows that persistent upconversion luminescence is essentially a super-delayed fluorescence from crystalline intermolecular charge-transfer excitons formed in the nonlinearly polarizable ferroelectric-like lattice. Magnetodielectrics indicate crystalline intermolecular charge-transfer excitons are coupled with nonlinearly polarizable ferroelectric-like lattice, leading to prolonged nonlinear optical behaviors shown as persistent upconversion luminescence through super delayed fluorescence. In conclusion, therefore, crystalline intermolecular charge-transfer excitons formed in nonlinearly polarizable ferroelectric-like lattice provide an interesting platform to generate prolonged nonlinear optical behaviors toward developing persistent upconversion luminescence under multiphoton excitation.

36 MATERIALS SCIENCE↗

π-Extended Ligands in Two-Coordinate Coinage Metal Complexes

Two-coordinate carbene-M I -amide (cMa, M I = Cu, Ag, Au) complexes have emerged as highly efficient luminescent materials for use in a variety of photonic applications, due to their extremely fast radiative rates via thermally activated delayed fluorescence (TADF) from an interligand charge transfer (ICT) process. A series of cMa derivatives were prepared to examine the variables which affect the radiative rate with the goal of understanding the parameters that control the radiative TADF process in these materials. We find that blue emissive complexes with high photoluminescence efficiency (Φ PL > 0.95) and fast radiative rates (k r = 4 x 10 6 s -1 ) can be achieved by selectively extending the π-system of the carbene and amide ligands. Of note is the role played by increasing the separation between the hole and electron in the ICT excited state. Analysis of temperature dependent luminescence data along with theoretical calculations indicate that the hole-electron separation alters the energy gap between the lowest energy singlet and triplet states (ΔE ST ) while keeping the radiative rate for the singlet state unchanged. As a result, this interpretation provides guidelines for the design of new cMa derivatives with even faster radiative rates as well as those with slower radiative rates and thus extended excited state lifetimes.

14 SOLAR ENERGY↗

Balancing Panchromatic Absorption and Multistep Charge Separation in a Compact Molecular Architecture

A panchromatic triad and a charge-separation triad are joined in a crossbar architecture to capture solar energy. The panchromatic triad (T) is comprised of a central free-base porphyrin that is strongly coupled via direct ethyne linkages to two perylene-monoimides. Here, the charge-separation unit incorporates a free-base or zinc chlorin (C or ZnC) as a hole acceptor (or electron donor) and a perylene-diimide (PDI) as an electron acceptor, both attached to the porphyrin via diphenylethyne linkers. The free-base porphyrin is common to both light-harvesting and charge-separation motifs. The chlorin and PDI also function as ancillary light absorbers, complementing direct excitation of the panchromatic triad to produce the discrete lowest excited state of the array (T*). Attainment of full charge separation across the pentad entails two steps: (1) an initial excited-state hole/electron transfer process to oxidize the chlorin (and reduce the triad) or reduce the PDI (and oxidize the triad); and (2) subsequent ground-state electron/hole migration to produce oxidized chlorin and reduced PDI. Full charge separation for pentad ZnC-T-PDI to generate ZnC + -T-PDI¯ occurs with a quantum yield of ~30% and mean lifetime ~1 μs in dimethyl sulfoxide. For C-T-PDI, initial charge separation is followed by rapid charge recombination. The molecular designs and studies reported here reveal the challenges of balancing the demands for charge separation (linker length and composition, excited-state energies, redox potentials, and medium polarity) with the constraints for panchromatic absorption (strong electronic coupling of the porphyrin and two perylene-monoimide units) for integrated function in solar-energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterisation of Specimens from a Former Soviet Thorium Processing Facility to Support Site Remediation

The former Prydniprovski Chemical Plant (PChP) is a large ex-soviet nuclear materials processing site of roughly 260 hectares, located in central Ukraine. PcHP was in operation between 1948 and 1991 for the purposes of processing uranium and thorium ore into ore concentrate. During its operational lifetime, tens of millions of tonnes of radioactive waste was generated on the site. A consequence of these activities, coupled with the mismanagement of the resulting radioactive materials and by-products, is that approximately 45% of the southern part of the site has become radioactively contaminated. This area comprises some 100-200 buildings and structures, many of which are in a state of disrepair and dereliction. Around 20 of these buildings are heavily radioactively contaminated, with radiation levels from a few μSv/hr to a maximum of 4 mSv/hr reported. The European Commission is currently working with the Ukraine Ministry of Energy and Coal Use and the Nuclear Regulator to improve radiological safety and security at the site. In order for these remediation works to proceed, the site management needs to characterise the radioactive materials that are held there. As part of this activity, the team from the University of Bristol have undertaken a survey of one of the most heavily contaminated buildings, collecting a selection of in situ material samples. A suite of complimentary materials characterisation techniques (e.g. X-ray Fluorescence, Raman Spectroscopy, etc) have been deployed in order to determine the radionuclides and composition of the compounds present. Characterisation of these samples will allow the operators of the chemical plant to go forward with remediation works within the building.

07 ISOTOPE AND RADIATION SOURCES↗

Search for photons above 10 18 eV by simultaneously measuring the atmospheric depth and the muon content of air showers at the Pierre Auger Observatory

The Pierre Auger Observatory is the most sensitive instrument to detect photons with energies above 1 0 17 eV . It measures extensive air showers generated by ultrahigh energy cosmic rays using a hybrid technique that exploits the combination of a fluorescence detector with a ground array of particle detectors. The signatures of a photon-induced air shower are a larger atmospheric depth of the shower maximum ( X max ) and a steeper lateral distribution function, along with a lower number of muons with respect to the bulk of hadron-induced cascades. In this work, a new analysis technique in the energy interval between 1 and 30 EeV ( 1 EeV = 1 0 18 eV ) has been developed by combining the fluorescence detector-based measurement of X max with the specific features of the surface detector signal through a parameter related to the air shower muon content, derived from the universality of the air shower development. No evidence of a statistically significant signal due to photon primaries was found using data collected in about 12 years of operation. Thus, upper bounds to the integral photon flux have been set using a detailed calculation of the detector exposure, in combination with a data-driven background estimation. The derived 95% confidence level upper limits are 0.0403, 0.01113, 0.0035, 0.0023, and 0.0021 km − 2 sr − 1 yr − 1 above 1, 2, 3, 5, and 10 EeV, respectively, leading to the most stringent upper limits on the photon flux in the EeV range. Compared with past results, the upper limits were improved by about 40% for the lowest energy threshold and by a factor 3 above 3 EeV, where no candidates were found and the expected background is negligible. The presented limits can be used to probe the assumptions on chemical composition of ultrahigh energy cosmic rays and allow for the constraint of the mass and lifetime phase space of super-heavy dark matter particles. Published by the American Physical Society 2024

79 ASTRONOMY AND ASTROPHYSICS↗