Vacuum Ultraviolet Research Articles

Photochemistry of micro-solvated benzonitrile complexes with water/ammonia bordering on the formation of icy grains

Polycyclic aromatic hydrocarbons (PAHs) act as condensation nuclei for water/ammonia molecules forming icy water clusters. In the context of small aromatic rings, we have theoretically examined complexes of benzonitrile with water/ammonia molecules in order to investigate the photochemical kinetics of the icy grain formation. First, we obtain the structure of energetically stable complexes containing different H-bonding patterns and analyze their effects in the infrared (IR) and vacuum ultraviolet (VUV) spectra, before and after ionization. Second, we evaluate the H-bonding reorientation kinetics of the complexes at low temperatures, which indicates that the process involving water occurs faster than the corresponding process involving ammonia. Finally, the thermal rate constants indicate which configurations are the most likely to be ionized under vacuum ultraviolet (VUV) irradiation. Our results are consistent with what has experimentally been observed for related complexes, and are useful as a starting point to investigate the process of the icy grains formation. This study provides insight into possible subsequent photochemical reactions occurring in the interstellar medium (ISM) or in jet-cooled molecular complexes.

FAT-GEMs: (field assisted) transparent gaseous-electroluminescence multipliers

The idea of implementing electroluminescence-based amplification through transparent multi-hole structures (FAT-GEMs) has been entertained for some time. Arguably, for such a technology to be attractive it should perform at least at a level comparable to conventional alternatives based on wires or meshes. We present now a detailed calorimetric study carried out for 5.9 keV X-rays in xenon, for pressures ranging from 2 to 10 bar, resorting to different geometries, production and post-processing techniques. At a reference voltage 5 times above the electroluminescence threshold (EEL,th ∼ 0.7 kV/cm/bar), the number of photoelectrons measured for the best structure was found to be just 18% below that obtained for a double-mesh with the same thickness and at the same distance. The energy resolution stayed within 10% (relative) of the double-mesh value. An innovative characteristic of the structure is that vacuum ultraviolet (VUV) transparency of the polymethyl methacrylate (PMMA) substrate was achieved, effectively, through tetraphenylbutadiene (TPB) coating of the electroluminescence channels combined with indium tin oxide (ITO) coating of the electrodes. This resulted in a × 2.25-increased optical yield (compared to the bare structure), that was found to be in good agreement with simulations if assuming a TPB wavelength-shifting-efficiency at the level of WLSE=0.74–1.28, compatible with expected values. This result, combined with the stability demonstrated for the TPB coating under electric field (over 20 h of continuous operation), shows great potential to revolutionize electroluminescence-based instrumentation.

Experimental setup for the measurement of optical properties in the vacuum ultraviolet region

Abstract This work presents an experimental setup designed for measuring optical properties in the vacuum ultraviolet (VUV) region. Originally developed for the characterization of ICARUS photomultiplier tubes, the setup has been recently employed to measure the conversion efficiency of para-Terphenyl coatings, acting as wavelength shifters, as a function of thickness. The VUV region is of particular interest in particle physics experiments utilizing cryogenic noble gases as scintillating media. The setup includes a deuterium light source, a mirror system, an intensity monitor, and a sample chamber to host sample and photodetector. An example measurement of para-Terphenyl conversion efficiency — as wavelength shifter — with varying thickness is presented, demonstrating the versatility and effectiveness of the presented system.

Efficient removal of size-fractionated antibiotic resistance genes (ARGs) in WWTPs secondary effluent by vacuum ultraviolet (VUV) activated potassium peroxymonosulfate (PMS)

Antibiotic resistance genes (ARGs) and mobile genetic elements (MGEs) in secondary effluent from wastewater treatment plants (WWTPs) have a size-fractionated character and conventional processes have difficulties in removing ARGs and MGEs. Therefore, this study aimed to explore the removal efficiency, removal mechanism and regeneration potential of size-fractionated ARGs and MGEs by vacuum ultraviolet (VUV)-activated peroxymonosulfate (PMS) and ascertain their potential hosts in secondary effluent. The proportion of particle-associated (PA)-ARGs and PA-MGEs was 85.07 %, followed by free-living (FL) fraction (14.91 %) and cell-free (CF) fraction (0.02 %). More than 95.00 %∼99.99 % of ARGs and MGEs in PA- and CF- fractions were removed by VUV/PMS, but the average removal efficiency of FL-ARGs and FL-MGEs was 66.15 %. Compared to the regeneration potential of PA- and CF-ARGs and MGEs (0.02 < C/C0 < 5.27), the regeneration occurred mainly in FL-ARGs and FL-MGEs (0.08 < C/C0 < 24.06). ·OH was the dominant radical (16.810 × 10-6 mol/L) in VUV/PMS for the removal of size-fractionated ARGs and MGEs from the secondary effluent, while SO4-· (4.478 × 10-6 mol/L) played a supporting role in the system based on the quenching experiment, electron paramagnetic resonance spectrometer and probe experiments. Based on full-scale classification, conditionally rare or abundant taxa (CRAT) were the core potential hosts in PA-, FL- and CF- fractions, while rare taxa (RT) and conditionally rare taxa (CRT) potential hosts were more diverse in the three fractions. This study suggests that VUV/PMS can effectively remove size-fractionated ARGs and MGEs from secondary effluent and thereby obviously reduce their dissemination risk to receiving water bodies, providing technical support for the engineering application of VUV/PMS in full-scale WWTPs.

Giant enhancement of second harmonic generation via merging bound states in the continuum for vacuum ultraviolet radiation

Vacuum ultraviolet (VUV) light plays a crucial role in various scientific and technological fields, such as nanolithography and biomedical treatments. However, the inherent nonlinear optical coefficient of nonlinear optical crystals is typically very low, and increasing the action length is often necessary to improve the nonlinear conversion efficiency. This makes it challenging for these materials to achieve high-density optoelectronic integration at the micro-/nano-scale. In this study, we propose a design for generating coherent VUV radiation close to 175 nm using second harmonic generation (SHG) with an absolute efficiency exceeding 1.2‰ mW−1. This is achieved by merging multiple bound state in the continuum modes in a free-standing photonic crystal slab. Even with fabrication imperfections at a level lower than 10% disorder, the SHG efficiency of the samples remains robust, maintaining an efficiency of at least 2‰. This research provides a beneficial platform for generating efficient VUV light in the nanoscale.

Luminescence Properties of an Orthorhombic KLaF4 Phosphor Doped with Pr3+ Ions under Vacuum Ultraviolet and Visible Excitation.

Fluorides have a wide bandgap and therefore, when doped with the appropriate ions, exhibit emissions in the ultraviolet C (UVC) region. Some of them can emit two photons in the visible region for one excitation photon, having a quantum efficiency greater than 100%. In a novel exploration, praseodymium (Pr3+) ions were introduced into KLaF4 crystals for the first time. The samples were obtained according to a high-temperature solid-state reaction. They exhibited an orthorhombic crystal structure, which has not been observed for this lattice yet. The optical properties of the material were investigated in the ultraviolet (UV) and visible ranges. The spectroscopic results were used to analyze the Pr3+ electronic-level structure, including the 4f5d configuration. It has been found that KLaF4:Pr3+ crystals exhibit intense luminescence in the UVC range, corresponding to multiple 4f → 4f transitions. Additionally, under vacuum ultraviolet (VUV) excitation, distinct transitions, specifically 1S0 → 1I6 and 3P0 → 3H4, were observed, which signifies the occurrence of photon cascade emission (PCE). The thermal behavior of the luminescence and the thermometric performance of the material were also analyzed. This study not only sheds light on the optical behavior of Pr3+ ions within a KLaF4 lattice but also highlights its potential for efficient photon management and quantum-based technologies.

Amorphous 1-propanol interstellar ice beyond its melting point

ABSTRACT The recent discovery of 1-propanol (CH3CH2CH2OH) in the interstellar medium (ISM) is of tremendous interest since fatty alcohols have been proposed as constituents of proto-cell membranes. Motivated by this discovery, we present the laboratory mid-infrared (MIR) and vacuum ultraviolet (VUV) absorption spectra of 1-propanol ice under astrochemical conditions, mimicking an icy mantle on cold dust in the ISM. Both MIR and VUV spectra were recorded at ultrahigh vacuum of ∼10-9 mbar and at temperatures ranging from 10 K to sublimation. The morphology of the 1-propanol ice deposited at 10 K was amorphous. By warming the ice to temperatures of 140 K and above, with subsequent recording of IR spectra, we observe complete sublimation of 1-propanol molecules from the substrate around 170 K. No amorphous-to-crystalline phase change was observed upon warming to higher temperatures. Additionally, we observe the IR and VUV signatures of 1-propanol ice on the substrate well beyond its melting point (147 K). To the best of our knowledge, this is the first reported observation of a molecular ice staying well beyond its melting point under such conditions. This result shows that the morphology of icy mantles on ISM cold dust grains is more complex than previously thought. Our atomistic molecular dynamics simulations capture the experimental trends and shed light on the microscopic origin of this unusual phase behaviour of 1-propanol.

High-Quality TiO2 Electron Transport Film Prepared via Vacuum Ultraviolet Illumination for MAPbI3 Perovskite Solar Cells.

The electron transport layer (ETL) plays an important role in determining the conversion efficiency and stability of perovskite solar cells (PSCs). Here, TiO2 thin film was prepared by irradiating diisopropoxy diacetylacetone titanium precursor thin film with 172 nm vacuum ultraviolet (VUV) at a low temperature. The prepared TiO2 thin film has higher electron mobility and conductivity. As it is used as an ETL for MAPbI3 PSCs, its band structure is better matched with the perovskite, and at the same time, due to the good interface contact, more uniform perovskite crystals are formed. Most importantly, a large number of hydroxyl radicals were formed during VUV irradiation of the precursor film, which made up for the oxygen defect present on the surface of the TiO2 thin film, and were adsorbed to the film surface. These hydroxyl groups form hydrogen bonds with methylammonium (MA) components on the MAPbI3 buried surface, thus promoting the transfer of photogenerated electrons at the MAPbI3/ETL interface. The power conversion efficiency of PSCs fabricated in air with the ETL prepared by VUV irradiation is 20.46%, which is higher than that of the contrast solar cell based on the sintered ETL (17.96%).

Wave packet dynamics and control in excited states of molecular nitrogen.

Wave packet interferometry with vacuum ultraviolet light has been used to probe a complex region of the electronic spectrum of molecular nitrogen, N2. Wave packets of Rydberg and valence states were excited by using double pulses of vacuum ultraviolet (VUV), free-electron-laser (FEL) light. These wave packets were composed of contributions from multiple electronic states with a moderate principal quantum number (n ∼ 4-9) and a range of vibrational and rotational quantum numbers. The phase relationship of the two FEL pulses varied in time, but as demonstrated previously, a shot-by-shot analysis allows the spectra to be sorted according to the phase between the two pulses. The wave packets were probed by angle-resolved photoionization using an infrared pulse with a variable delay after the pair of excitation pulses. The photoelectron branching fractions and angular distributions display oscillations that depend on both the time delays and the relative phases of the VUV pulses. The combination of frequency, time delay, and phase selection provides significant control over the ionization process and ultimately improves the ability to analyze and assign complex molecular spectra.

Nonadiabatic Molecular Dynamics of Water Cluster Dissociation by Vacuum Ultraviolet Absorption or Electron Impact Excitation.

After five decades of investigation since the 1970s, the nature of photon-induced or electron-induced water dissociation is still largely studied only in the gas phase, with a notable absence of dynamics studies of water clusters and bulk water. We study the problem with density functional theory and the nonadiabatic fewest switches surface hopping technique considering both singlet and triplet excited states to study the dissociation of water clusters leading mainly to OH + H. For clusters of 40 water molecules, the mean dissociation time was found to be <10 fs, and the threshold energy was ∼6 eV. Dissociation is almost exclusively associated with the cluster surface due to the lower energy of surface water excited states relative to the bulk. Recombination plays a major role in vacuum ultraviolet dissociation. O + H2 is found as a minor product in the dissociation and is mostly produced in "roaming" trajectories.

Closing the loop in space 3D printing: Effect of vacuum, recycling, and UV aging on high performance thermoplastics produced via filament extrusion additive manufacturing

The outlook for space exploration, and the long-term sustainable presence of humans in space, rely upon the advancement of in-situ manufacturing capabilities. In-space additive manufacturing (AM) has gained significant attention due to its potential to produce spare parts in-situ and facilitate repairs for extending space missions. However, to date, there is no AM system capable of processing high-performance engineering thermoplastic polymers within uncontrolled space conditions (i.e., reduced gravity, vacuum, and radiation environment). Additionally, the effect of ultra-violet (UV) radiation on printed parts has remained unexplored. In this work, a custom-built filament extrusion AM breadboard has been developed and tested enabling the fabrication of engineering thermoplastic polymers, whereby the machine was placed inside a vacuum chamber to partly mimic the harsh space environment. Mechanical (tensile and flexural) and thermal (thermogravimetric analysis, differential scanning calorimetry and dynamic mechanical analysis) tests were conducted on the printed specimens before and after exposure to UV aging. Moreover, the printed geometries underwent a recycling process involved the shredding of the pristine 3D-printed polymeric samples, the drying of the obtained granulates and finally the extrusion of 3D-printable filaments. The polymeric recycled 3D-printed specimens were then subjected to further mechanical and thermal testing, offering valuable insights into the feasibility of in-space AM and the potential to augment the circularity of the printed parts. The results of the mechanical and thermal tests, together with the effect of vacuum printing, UV aging, and recycling, are provided within the manuscript. This work cements the basic building blocks to sustainably advance on-orbit and in-space infrastructure, and paves the way for long-term human space missions.

Performance and oxidation mechanism of VUV photo–Fenton in simultaneous removal of Ni-EDTA and hypophosphite: decomplexation, low-valent phosphorous oxidation and DFT calculation

The photo–Fenton process offers a promising alternative for the oxidation of complex heavy metals. However, the potential influence of coexisting substrates may be overlooked. The •OH radicals generated in the photo–Fenton process ensure superior oxidation ability. In this study, we used a vacuum ultraviolet (VUV) light-assisted photo–Fenton (VPF) process to explore its performance in the synergistic oxidation of Ni-ethylenediaminetetraacetic acid (EDTA) and coexisting hypophosphite, typical pollutants in electroless nickel plating (ENP) wastewater. Based on electron spin resonance (ESR) and DMSO-probing results, •OH was the predominant reactive oxygen species, and VPF possessed the highest •OH concentration compared to other photochemical processes under identical conditions (pH, Fe, H2O2). Enhanced •OH generation in VPF was attributed to various photochemical reactions, including photo–Fenton, UV/H2O2, and VUV/H2O. Consequently, VPF exhibited efficient Ni-EDTA decomplexation and hypophosphite oxidation. Notably, the evolution and rate-limiting steps during hypophosphite oxidation were demonstrated by experimental results and density functional theory calculations. Hypophosphite was initially oxidized to phosphite, which subsequently oxidized to phosphate. The oxidation of phosphite could be considered the rate-limiting step as it exhibits higher energy barriers than hypophosphite oxidation. Adequate •OH generation in the VPF process could overcome this energy barrier, indicating its potential for application in pollutant removal and resource recovery from ENP wastewater.

Vacuum Ultraviolet Single Photon Ionization and Decomposition of 2-Aminopropionitrile in Astrophysical Objects

The molecule 2-aminopropionitrile (2-APN; H3CCH(NH2)CN) is a chiral precursor of the amino acid alanine and could play an important role in the emergence of the homochirality of life. To date, 2-APN has not yet been detected in the interstellar medium. To address the question of its absence, possibly through destruction by vacuum ultraviolet radiation in astrophysical media, we studied its photoionization and dissociative photoionization in the 9–14 eV (89–137 nm) energy range using photoelectron–photoion coincidence spectroscopy with velocity map imaging. Density functional theory calculations were performed at the PBE0/aug-cc-pVTZ level to determine structures for the various cationic fragments identified experimentally. Their appearance energies were calculated. The adiabatic ionization energy (AIE) of 2-APN is AIE = (9.85±0.01) eV and the appearance energy (AE) of the major fragment ion N≡CC(H)NH2 + is AE = (10.57±0.01) eV. Both ions, 2-APN+ and N≡CC(H)NH2 +, make up more than 90% of the formed ions. N≡CC(H)NH2 +, an isomer of the protonated HCN dimer, is also formed with high yield in the dissociative photoionization of aminoacetonitrile (NH2CH2CN), another α-aminonitrile observed in Sgr B2(N). Photoion yield spectra have been calibrated to absolute ionization cross sections. From these, we derive photoionization rates in several typical radiation fields relevant to different astrophysical objects. The rates show that, under almost all explored radiation fields, dissociative ionization is the dominant pathway for photoionization, leading to the loss of a methyl group (CH3) to form the planar thermodynamically stable amino cyano methylidynium ion N≡CC(H)NH2 +. The observed absence of 2-APN in Sgr B2 could thus be due to dominant dissociative photoionization.

Conformer-Specific Photoelectron Spectroscopy of Carbonic Acid: H2CO3.

Carbonic acid (H2CO3) is a fundamental species in biological, ecological, and astronomical systems. However, its spectroscopic characterization is incomplete because of its reactive nature. The photoionization (PI) and the photoion mass-selected threshold photoelectron (ms-TPE) spectra of H2CO3 were obtained by utilizing vacuum ultraviolet (VUV) synchrotron radiation and double imaging photoelectron photoion coincidence spectroscopy. Two carbonic acid conformers, namely, cis-cis and cis-trans, were identified. Experimental adiabatic ionization energies (AIEs) of cis-cis and cis-trans H2CO3 were determined to be 11.27 ± 0.02 and 11.18 ± 0.03 eV, and the cation enthalpies of formation could be derived as ΔfH°0K = 485 ± 2 and 482 ± 3 kJ mol-1, respectively. The cis-cis conformer shows intense peaks in the ms-TPES that are assigned to the C=O/C-OH stretching mode, while the cis-trans conformer exhibits a long progression to which two C=O/C-OH stretching modes contribute. The TPE spectra allow for the sensitive and conformer-selective detection of carbonic acid in terrestrial experiments to better understand astrochemical reactions.

AlN Thin-Film Vacuum Ultraviolet Photodetector With High Operating Temperature and High Rejection Ratio

AlN Thin-Film Vacuum Ultraviolet Photodetector With High Operating Temperature and High Rejection Ratio

Photoionization of Nitrile-substituted Naphthalene and Benzene: Cation Spectroscopy, Photostability, and Implications for Photoelectric Gas Heating

We investigate the vacuum ultraviolet (VUV) photodynamics of gas phase 1- and 2-cyanonaphthalene and cyanobenzene, recently detected in the Taurus molecular cloud, by combining synchrotron radiation and a double imaging electron/ion coincidence setup. The high-resolution threshold photoelectron spectra (TPES) of all three molecules are obtained experimentally from which the adiabatic ionization energies are reported with very high accuracy, particularly for 2-cyanonaphthalene, for which no data exist at this level of precision. Theoretical calculations are performed to compare with the TPES for the ground electronic state of the cations. Furthermore, the different features observed in the extended TPES have been assigned to the different molecular orbitals with the help of the outer valence Green's function calculations. The present experiments also shed light on the kinetic energy distribution of the photoelectrons as a function of the incident photon energy, to describe their contribution to the photoelectric heating effect in the interstellar medium. In this context, we show how kinetic energy distributions can be obtained from our data for any given photon energy, such as the omnipresent Lyα line, or any given interstellar radiation field (ISRF). In addition, from the total ion yields, we estimate the photorates for a few ISRFs. Finally, we discuss the photodissociation of the two cyanonaphthalenes, quoting the activation energies of the dissociation channels with the help of Rice–Ramsperger–Kassel–Marcus modeling. It is observed that CN substitution does not cause any appreciable change to the VUV dissociative photoionization relaxation channel.

Efficient Oxidative Decomposition of Jet-Fuel exo-Tetrahydrodicyclopentadiene (JP-10) by Aluminum Nanoparticles in a Catalytic Microreactor: An Online Vacuum Ultraviolet Photoionization Study.

The oxidation of gas-phase exo-tetrahydrodicyclopentadiene (JP-10, C10H16) over aluminum nanoparticles (AlNP) has been explored between a temperature range of 300 and 1250 K with a novel chemical microreactor. The results are compared with those obtained from chemical microreactor studies of helium-seeded JP-10 and of helium-oxygen-seeded JP-10 without AlNP to gauge the effects of molecular oxygen and AlNP, respectively. Vacuum ultraviolet (VUV) photoionization mass spectrometry reveals that oxidative decomposition of JP-10 in the presence of AlNP is lowered by 350 and 200 K with and without AlNP, respectively, in comparison with pyrolysis of the fuel. Overall, 63 nascent gas-phase products are identified through photoionization efficiency (PIE) curves; these can be categorized as oxygenated molecules and their radicals as well as closed-shell hydrocarbons along with hydrocarbon radicals. Quantitative branching ratios of the products reveal diminishing yields of oxidized species and enhanced branching ratios of hydrocarbon species with the increase in temperature. While in the low-temperature regime (300-1000 K), AlNP solely acts as an efficient heat transfer medium, in the higher-temperature regime (1000-1250 K), chemical reactivity is triggered, facilitating the primary decomposition of the parent JP-10 molecule. This enhanced reactivity of AlNP could plausibly be linked to the exposed reactive surface of the aluminum (Al) core generated upon the rupture of the alumina shell material above the melting point of the metal (Al).

Atmospheric pressure argon plasma jets I – Measurements of spatial distribution for visible emission spectrum and vacuum ultraviolet

AbstractThis paper describes the observed position dependent emission spectrum and vacuum ultraviolet (VUV) to clarify the optical structure of argon atmospheric pressure plasma jets (APJs). Visible emission spectra of argon, nitrogen, and OH molecules were measured as a function of position from the nozzle of plasma jet generator to gas flow direction. From the results, we realized that a certain electric field is required for producing high energy excited atoms of argon in the jet from the high voltage electrode in the device to the ground positioned at downstream side. Moreover, VUV was detected along the plasma jet through the downstream direction. Thus, we could picture that the light pattern of plasma jet of which intensity weaken depend to the distance from the nozzle is sustained by the above two factors with the present steady state experiments.

Structures and Properties of High-Concentration Doped Th:CaF2 Single Crystals for Solid-State Nuclear Clock Materials.

Thorium-doped vacuum ultraviolet (VUV) transparent crystals is a promising candidate for establishing a solid-state nuclear clock. Here, we report the research results on high-concentration doping of 232Th:CaF2 single crystals. The structures, defects, and VUV transmittance performances of highly doped Th:CaF2 crystals are investigated by theoretical and experimental methods. The defect configurations formed by Th and the charge compensation mechanism (Ca vacancy or interstitial F atoms) located at its first nearest neighbor position are mainly considered and studied. The preferred defect configuration is identified according to the doping concentration dependence of structural changes caused by the defects and the formation energies of the defects at different Ca or F chemical potentials. The cultivated Th:CaF2 crystals maintain considerable high VUV transmittance levels while accommodating high doping concentrations, showcasing an exceptional comprehensive performance. The transmittances of 1-mm-thick samples with doping concentrations of 1.91 × 1020 and 2.76 × 1020 cm-3 can reach ∼62% and 53% at 150 nm, respectively. The VUV transmittance exhibits a weak negative doping concentration dependence. The system factors that may cause distortion and additional deterioration of the VUV transmittance are discussed. Balancing and controlling the impacts of various factors will be of great significance for fully exploiting the advantages of Th:CaF2 and other Th-doped crystals for a solid-state nuclear optical clock.

Absolute Photoionization Cross Section and Dissociative Ionization Pathways of Alpha-Pinene.

The absolute photoionization cross section of the monoterpenoid, alpha-pinene (AP), is presented together with the relative photoionization cross sections of its dissociative fragments for the first time. Experiments are performed via multiplexed vacuum ultraviolet (VUV) synchrotron photoionization (PI) mass spectrometry in the 8.0-11.0 eV energy range. Experimental work is conducted at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Dissociative fragments were identified at m/z 121, 94, 93, 92, and 80. The photoionization cross section for the parent mass at 11.0 eV was determined to be 17±4 Mb with a total ionization cross section of 92±23 Mb at the same photon energy. Experimental appearance energies of dissociative ionization fragments and potential dissociative ionization pathways calculated at the G4 level of theory are presented as well.