Photoabsorption Cross Sections Research Articles

On the valence shell spectroscopy of 1,2-dichlorobenzene

We report high-resolution vacuum ultraviolet (VUV) photoabsorption spectrum of 1,2-dichlorobenzene in the photon energy range 4.0–10.8 eV (310–115 nm). The electronic state spectroscopy of ortho-C6H4Cl2 has been investigated together with quantum chemical calculations at different levels of theory, also providing vertical excitation energies and oscillator strengths. The valence, mixed valence-Rydberg and Rydberg character of the electronic transitions is accompanied by fine structure which has been mainly assigned to in-plane breathing with C–Cl stretching, v7′a1, ring breathing and C–C stretching, v8′a1, in-plane ring breathing, v9′a1, C–Cl symmetric stretching, v10′a1, and in-plane C–Cl bending v11′a1 modes. The experimental absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of 1,2-dichlorobenzene in the Earth’s atmosphere (0–50 km), showing that solar photolysis is expected to be a weak sink at altitudes lower than 20 km relative to OH radical reactions. Potential energy curves for the lowest-lying excited electronic states, as a function of the C–Cl stretching and in-plane C–Cl bending coordinates, were also obtained employing the time dependent density functional theory (TD-DFT) method. The results show the importance of the complex quasi-degenerate nature of the lowest-lying electronic states which in the intricate nuclear dynamics of the reaction coordinates, yield relevant internal conversion from Rydberg to valence character and in the asymptotic limit bond excision.

Giant dipole resonance parameters optimization and photo-neutron cross-section calculations of several spherical and deformed nuclei

Understanding the interaction between photons and matter is crucial for exploring essential questions in nuclear physics. The Giant Dipole Resonance (GDR) is the prevailing mechanism in photo-absorption cross-sections up to 30 MeV. Depending on whether the nucleus is spherical or deformed, the curve of the photo-absorption cross-section versus photon energy is characterized by one or several Lorentzian peaks. Theoretical calculations of photo-absorption cross-sections are largely centered on deducing GDR parameters. These parameters are used in theoretical reaction codes that aim to simulate photon-induced nuclear reactions accurately. In this study, the GDR parameters for the spherical isotopes 115In, 144Sm, 148Sm, 150Sm, and for the deformed isotopes 154Sm, 153Eu, and 160Gd were calculated by optimizing to the experimental data. The calculated GDR parameters were inputted into the TALYS 1.8 code to compute the photo-neutron cross sections, which were then compared with experimental results from the literature. It has been observed that the calculations performed with the obtained GDR parameters are consistent with the experimental data.

The electric dipole characteristics of well-deformed 171,173Yb

The electric dipole response of well-deformed 171,173Yb in the giant dipole resonance (GDR) and pygmy dipole resonance (PDR) range has been theoretically analyzed using the translation and Galileo invariant quasiparticle phonon nuclear model (TGI-QPNM). The TGI-QPNM consists of an axially symmetric Woods-Saxon Potential, monopole pairing, dipole-dipole residual interaction, and the restoration terms for broken translation and Galilean symmetries. Numerical calculations show the existence of considerable E1 excitations around the neutron separation threshold (S n ) in both isotopes. The TGI-QPNM results of the photoabsorption cross-section give a double-humped shape in both nuclei, consistent with the available experimental data. The integrated moments (σ 0, σ −1) and the centroid energies in the GDR region are also reproduced well.

Valence shell electronically excited states of 1-phenylimidazole and 1-benzylimidazole

The valence shell electronically excited states of 1-phenylimidazole and 1-benzylimidazole have been studied by employing synchrotron radiation to measure the absolute photoabsorption cross-section of each molecule, from threshold up to an energy of 10.8 eV. Assignments have been proposed for some of the broad absorption bands using calculated transition energies and oscillator strengths. Natural transition orbital plots have allowed the Rydberg and/or valence character of the electronically excited states to be assessed. Some of the calculated transitions in 1-benzylimidazole and 1-phenylimidazole have initial and final orbitals that are analogous to those of transitions in the isolated constituent rings of imidazole and benzene. Other mixed Rydberg/valence transitions, especially those leading to some of the low energy electronically excited states in 1-phenylimidazole, have an initial orbital located on the imidazole ring while valence character in the final orbital is localised on the phenyl ring. Thus, photoexcitation results in charge transfer from the donor site (imidazole) to the acceptor (the phenyl ring) in the nascent ion core of the Rydberg state. In both 1-benzylimidazole and 1-phenylimidazole the lowest energy excited state arises from a transition analogous to the 1e1g → 1e2u 1B2u electric dipole-forbidden transition in benzene.

Electric dipole polarizability of low-lying excited states in atomic nuclei

New equations for the electric dipole polarizability α E1 of low-lying excited states in atomic nuclei—and the related (−2) moment of the total photo-absorption cross section, σ −2—are inferred in terms of electric dipole and quadrupole matrix elements. These equations are valid for arbitrary angular momenta of the initial/ground and final/excited states and have been exploited in fully converged 1ℏ ω shell-model (SM) calculations of selected p- and sd-shell nuclei that consider configuration mixing; advancing previous knowledge from 17O to 36Ar, where thousands of electric dipole matrix elements are computed from isovector excitations which include the giant dipole resonance (GDR) region. Our results are in reasonable agreement with previous SM calculations and follow—except for 6,7Li and 17,18O—Migdal’s global trend provided by the combination of the hydrodynamic model and second-order non-degenerate perturbation theory. Discrepancies in 6,7Li and 17O arise as a result of the presence of α-cluster configurations in odd-mass nuclei, whereas the disagreement in 18O comes from the mixing of intruder states, which is lacking in the SM interactions. More advanced ab initio calculations of the dipole polarizability for low-lying excited states covering all the isovector states within the GDR region are missing and could be very valuable to benchmark the results presented here and shed further light on how atomic nuclei polarize away from the ground state

Photoabsorption cross section measurements of acetylene in the nonionizing region using the double-ion chamber method

The double-ion chamber (DIC) method has been used to measure photoabsorption cross sections in the ionization region of the sample gas. In this study, we introduce a method to extend the wavelength region of the DIC measurements beyond the ionization threshold wavelength by using the photoion currents from the impurities in the sample gas. To verify this method, the photoabsorption cross sections of C2H2 (ionization threshold wavelength λth = 108.8 nm) have been measured from 105 to 137 nm. The natural impurity, acetone (λth = 127.8 nm), contained 1% in high-purity grade acetylene (C2H2) sample gas, allowing for measurements in the non-ionizing region of C2H2 up to 127.7 nm. By adding 1% benzene (λth = 134.6 nm) in the sample gas, measurements were possible even further, to 134.5 nm. This new method enables the measurement of the photoabsorption cross section by photoions that are produced from the impurities in the sample gas in a substantial amount. The current measurement methodology aligns well with the previous measurements of Suto and Lee [Suto and Lee, J. Chem. Phys. 80, 4824 (1984)].

High-quality lateral monolayer-multilayer graphene junction formed by selective laser thinning for self-powered photodetection

The formation of an asymmetric junction is key to graphene-based photodetectors of high-sensitive photodetectability, because such a junction can not only facilitate the diffusion or drift of photogenerated carriers but also realize a self-powered operation. Here, a monolayer-multilayer graphene junction photodetector is accomplished by selectively thinning part of a multilayer graphene to a high-quality monolayer. Benefiting from the large photoabsorption cross section of multilayer graphene and strong asymmetry caused by the significant differences in optoelectronic properties between monolayer and multilayer graphene, the monolayer-multilayer graphene junction shows a 7-fold increase in short-circuit photocurrent as compared with that at the monolayer graphene-metal contact in scanning photocurrent images. The asymmetric configuration also enables the photodetector to work at zero bias with minimized dark current noise and stand-by power consumption. Under global illumination with visible light, a photoswitching ratio of 3.4 × 103, a responsivity of 8.8 mA W−1, a specific detectivity of 1.3 × 108 Jones and a response time of 11 ns can be obtained, suggesting a promising photoresponse. Moreover, it is worth mentioning that such a performance enhancement is achieved without compromising the broadband spectral response of graphene photodetector and it is hence applicable for long wavelength spectral range including infrared and terahertz.

Photodissociation dynamics of SO2 via the G̃1B1 state: The O(1D2) and O(1S0) product channels.

Produced by both nature and human activities, sulfur dioxide (SO2) is an important species in the earth's atmosphere. SO2 has also been found in the atmospheres of other planets and satellites in the solar system. The photoabsorption cross sections and photodissociation of SO2 have been studied for several decades. In this paper, we reported the experimental results for photodissociation dynamics of SO2 via the G̃1B1 state. By analyzing the images from the time-sliced velocity map ion imaging method, the vibrational state population distributions and anisotropy parameters were obtained for the O(1D2) + SO(X3Σ-, a1Δ, b1Σ+) and O(1S0) + SO(X3Σ-) channels, and the branching ratios for the channels O(1D2) + SO(X3Σ-), O(1D2) + SO(a1Δ), and O(1D2) + SO(b1Σ+) were determined to be ∼0.3, ∼0.6, and ∼0.1, respectively. The SO products were dominant in electronically and rovibrationally excited states, which may have yet unrecognized roles in the upper planetary atmosphere.

A Missing Piece of the E‐Region Puzzle: High‐Resolution Photoionization Cross Sections and Solar Irradiances in Models

AbstractMost ionospheric models cannot sufficiently reproduce the observed electron density profiles in the E‐region ionosphere, since they usually underestimate electron densities and do not match the profile shape. Mitigation of these issues is often addressed by increasing the solar soft X‐ray flux which is ineffective for resolving data‐model discrepancies. We show that low‐resolution cross sections and solar spectral irradiances fail to preserve structure within the data, which considerably impacts radiative processes in the E‐region, and are largely responsible for the discrepancies between observations and simulations. To resolve data‐model inconsistencies, we utilize new high‐resolution (0.001 nm) atomic oxygen (O) and molecular nitrogen (N2) cross sections and solar spectral irradiances, which contain autoionization and narrow rotational lines that allow solar photons to reach lower altitudes and increase the photoelectron flux. This work improves upon Meier et al. (2007, https://doi.org/10.1029/2006gl028484) by additionally incorporating high‐resolution N2 photoionization and photoabsorption cross sections in model calculations. Model results with the new inputs show increased O+ production rates of over 500%, larger than those of Meier et al. (2007, https://doi.org/10.1029/2006gl028484) and total ion production rates of over 125%, while production rates decrease by ∼15% in the E‐region in comparison to the results obtained using the cross section compilation from Conway (1988, https://apps.dtic.mil/sti/pdfs/ADA193866.pdf). Low‐resolution molecular oxygen (O2) cross sections from the Conway compilation are utilized for all input cases and indicate that is a dominant contributor to the total ion production rate in the E‐region. Specifically, the photoionization contributed from longer wavelengths is a main contributor at ∼120 km.

A study on the resist performance of inorganic-organic resist materials for EUV and electron-beam lithography

In the realization of further miniaturization at scales of 10 nm and below in semiconductor devices, it is essential to create new resist designs, such as hybrid inorganic-organic resist materials for ionizing radiation, in order to clarify the effect the structure of metal resist on resist performance. In this study, some hybrid inorganic-organic resist materials known as metal-oxo clusters were synthesized, and their lithographic characteristics were investigated to clarify the relationship between resist performance, such as sensitivity, resolution, and their absorption coefficient or cross section, and the density of their elements by using EUV and electron-beam (EB) exposure. Our results indicated that the sensitivity in Hf-based oxo clusters was higher than that of Ti-based and Zr-based oxo clusters in both EB and EUV exposure. Although the exposure dose was not optimized, the patterns of Ti-based, Zr-based, and Hf-based oxo clusters showed 100, 50, and 32 nm line-and-space patterns at doses of 250, 80, and 25 μC cm−2, respectively. We clarified that it is very important for new resist designs such as hybrid inorganic-organic resists to increase the photo-absorption cross section and density of elements for EUV and EB without degradation of film quality. In addition, the size and homogeneity of the building blocks and film quality are very important for the resist performance of hybrid inorganic-organic resist materials. Furthermore, it is clarified that the etch durability of metal-oxo clusters is higher than conventional resist materials, and this is much increased by annealing them at 800 °C.

Xenon photonuclear cross sections for the production of 123I radionuclide

A simple reliable theoretical model for the calculation of total photo-absorption cross sections by atomic nuclei has been presented and applied it to get the relevant data needed for the evaluation of the production rate of 123I radionuclide isotope. Since experimental measurements are not available, the model calculation represents the only source of information. The present results, based on an accurate model of nuclear structure, are in very good agreement with the observed photoabsorption cross sections of Te isotopes, which provide reliable cross sections for the neighboring Xe nuclei, where the usual simple estimates are clearly discordant.

Toward a new approach for the pygmy dipole resonance in even–even nuclei. Application to isotopes 144,148,150,152,154Sm

A many-body Hamiltonian consisting of a spherical shell model mean-field term, a pairing interaction for alike nucleons and a dipole–dipole interaction, with the dipole operator involving a cubic term in the radial coordinate, was studied within a quasiparticle random-phase approximation and applied numerically to five even–even isotopes of Sm. The resulting wavefunctions were further used to calculate the B(E1) values, which at their turn were employed to calculate the photoabsorption cross section, integrated moments of the cross section and energy weighted sum rule (EWSR). The calculated cross section and its integrated moments were compared with the available data, and a good agreement was observed. Two regions were distinguished: one corresponding to the pygmy dipole resonance (PDR) (1–10 MeV) and the other to the giant dipole resonance (GDR) (10–20 MeV), which were studied separately. The peaks belonging to each of the two ranges were analyzed in detail. The PDR states were located around the neutron separation energy and were mainly formed by the collective isoscalar and neutron collective states. The PDR states describe oscillations of the neutron excess against protons from the isospin-saturated core. The character of the states from the GDR region, isoscalar or isovector, is also pointed out. The PDR states carry only 0.8%–2.7% of the total EWSR and 0.4%–5.9% of the total E1 strength. The dependence of the dipole strength on nuclear deformation is evidenced. A comment on the cross section splitting into two branches for deformed isotopes is included. The r-cubic term and nuclear deformation have opposite effects on the dipole strength. In addition, it diminishes the effect of nonconservation of the center of mass momentum. The famous Thomas–Reiche–Kuhn sum rule formula is generalized to the case of the Schiff dipole momentum. The new sum rule is well satisfied. The projected spherical single-particle basis used in our formalism allows for a unified description of spherical transitional and deformed isotopes.

Signatures of X-Ray-dominated Chemistry in the Spectra of Exoplanetary Atmospheres

High-energy radiation from stars impacts planetary atmospheres, deeply affecting their chemistry and providing departures from chemical equilibrium. While the upper atmospheric layers are dominated by ionizations induced by extreme-ultraviolet radiation, deeper into the atmosphere, molecular abundances are controlled by a characteristic X-ray-dominated chemistry, mainly driven by an energetic secondary electron cascade. In this work, we aim at identifying molecular photochemically induced fingerprints in the transmission spectra of a giant planet atmosphere. We have developed a numerical code capable of synthesizing transmission spectra with arbitrary spectral resolution, exploiting updated infrared photoabsorption cross sections. Chemical mixing ratios are computed using a photochemical model tailored to investigate high-energy ionization processes. We find that in the case of high levels of stellar activity, synthetic spectra in both low and high resolutions show significant, potentially observable out-of-equilibrium signatures arising mainly from CO, CH4, C2H2, and HCN.

Valence shell electronically excited states of norbornadiene and quadricyclane.

The absolute photoabsorption cross sections of norbornadiene (NBD) and quadricyclane (QC), two isomers with chemical formula C7H8 that are attracting much interest for solar energy storage applications, have been measured from threshold up to 10.8eV using the Fourier transform spectrometer at the SOLEIL synchrotron radiation facility. The absorption spectrum of NBD exhibits some sharp structure associated with transitions into Rydberg states, superimposed on several broad bands attributable to valence excitations. Sharp structure, although less pronounced, also appears in the absorption spectrum of QC. Assignments have been proposed for some of the absorption bands using calculated vertical transition energies and oscillator strengths for the electronically excited states of NBD and QC. Natural transition orbitals indicate that some of the electronically excited states in NBD have a mixed Rydberg/valence character, whereas the first ten excited singlet states in QC are all predominantly Rydberg in the vertical region. In NBD, a comparison between the vibrational structure observed in the experimental 11B1-11A1 (3sa1 ← 5b1) band and that predicted by Franck-Condon and Herzberg-Teller modeling has necessitated a revision of the band origin and of the vibrational assignments proposed previously. Similar comparisons have encouraged a revision of the adiabatic first ionization energy of NBD. Simulations of the vibrational structure due to excitation from the 5b2 orbital in QC into 3p and 3d Rydberg states have allowed tentative assignments to be proposed for the complex structure observed in the absorption bands between ∼5.4 and 7.0eV.

Data availability and requirements relevant for the Ariel space mission and other exoplanet atmosphere applications

ABSTRACT The goal of this white paper is to provide a snapshot of the data availability and data needs primarily for the Ariel space mission, but also for related atmospheric studies of exoplanets and cool stars. It covers the following data-related topics: molecular and atomic line lists, line profiles, computed cross-sections and opacities, collision-induced absorption and other continuum data, optical properties of aerosols and surfaces, atmospheric chemistry, UV photodissociation and photoabsorption cross-sections, and standards in the description and format of such data. These data aspects are discussed by addressing the following questions for each topic, based on the experience of the ‘data-provider’ and ‘data-user’ communities: (1) what are the types and sources of currently available data, (2) what work is currently in progress, and (3) what are the current and anticipated data needs. We present a GitHub platform for Ariel-related data, with the goal to provide a go-to place for both data-users and data-providers, for the users to make requests for their data needs and for the data-providers to link to their available data. Our aim throughout the paper is to provide practical information on existing sources of data whether in data bases, theoretical, or literature sources.

Heteroepitaxy in Organic/TMD Hybrids and Challenge to Achieve it for TMD Monolayers: The Case of Pentacene on WS2 and WSe2.

The intriguing photophysical properties of monolayer stacks of different transition-metal dichalcogenides (TMDs), revealing rich exciton physics including interfacial and moiré excitons, have recently prompted an extension of similar investigations to hybrid systems of TMDs and organic films, as the latter combine large photoabsorption cross sections with the ability to tailor energy levels by targeted synthesis. To go beyond single-molecule photoexcitations and exploit the excitonic signatures of organic solids, crystalline molecular films are required. Moreover, a defined registry on the substrate, ideally an epitaxy, is desirable to also achieve an excitonic coupling in momentum space. This poses a certain challenge as excitonic dipole moments of organic films are closely related to the molecular orientation and film structure, which critically depend on the support roughness. Using X-ray diffraction, optical polarization, and atomic force microscopy, we analyzed the structure of pentacene (PEN) multilayer films grown on WSe2(001) and WS2(001) and identified an epitaxial alignment. While (022)-oriented PEN films are formed on both substrates, their azimuthal orientations are quite different, showing an alignment of the molecular L-axis along the and directions. This intrinsic epitaxial PEN growth depends, however, sensitively on the substrates surface quality. While it occurs on exfoliated TMD single crystals and multilayer flakes, it is hardly found on exfoliated monolayers, which often exhibit bubbles and wrinkles. This enhances the surface roughness and results in (001)-oriented PEN films with upright molecular orientation but without any azimuthal alignment. However, monolayer flakes can be smoothed by AFM operated in contact mode or by transferring to ultrasmooth substrates such as hBN, which again yields epitaxial PEN films. As different PEN orientations result in different characteristic film morphologies (elongated mesa islands vs pyramidal dendrites), which can be easily distinguished by AFM or optical microscopy, this provides a simple means to judge the roughness of the used TMD surface.

The electronic structure of 2(5H)-thiophenone investigated by vacuum ultraviolet synchrotron radiation and theoretical calculations

The electronic state spectroscopy of 2(5H)-thiophenone, C4H4OS, has been investigated by high-resolution vacuum ultraviolet photoabsorption in the 3.76–10.69 eV energy range using synchrotron radiation, together with novel quantum chemical calculations performed at the equation of motion coupled cluster singles and doubles (EOM-CCSD) level of theory. The major electronic transitions have been assigned to valence and Rydberg character, with relevant C=O, C=C and C–C stretching vibrations across the entire absorption spectrum. Photolysis lifetimes in the Earth’s atmosphere (0–50 km altitude) have been estimated from the absolute photoabsorption cross-sections, indicating that solar photolysis can be expected to be a strong sink mechanism.Graphical abstract

Valence and Rydberg excitations of 3-fluorotoluene in the 4.4–10.8 eV photoabsorption energy region

The absolute photoabsorption cross sections for 3-fluorotoluene in the 4.4–10.8 eV energy-range were obtained for the first-time using a synchrotron radiation light source. New theoretical calculations, providing vertical excitation energies and oscillator strengths, were performed at the time-dependent density functional theory and the equation-of-motion coupled cluster method restricted to single and double excitations to qualitatively support the experimental data. The electronic transitions discernible in the photoabsorption spectrum have been assigned to valence, mixed valence-Rydberg and Rydberg transitions. Additionally, a comprehensive assignment of the vibronic structure was performed with the main contribution of C–H in plane bending mode progressions dictating the spectroscopy of the lowest-lying absorption band. From the absolute photoabsorption cross sections, the photolysis lifetimes of 3-fluorotoluene in the Earth's atmosphere were also obtained.

Validation of E‐Region Model Electron Density Profiles With AURIC Utilizing High‐Resolution Cross Sections

AbstractE‐region models have traditionally underestimated the ionospheric electron density. We believe that this deficiency can be remedied by using high‐resolution photoabsorption and photoionization cross sections in the models. Deep dips in the cross sections allow solar radiation to penetrate deeper into the E‐region producing additional ionization. To validate our concept, we perform a study of model electron density profiles (EDPs) calculated using the Atmospheric Ultraviolet Radiance Integrated Code (AURIC; D. Strickland et al., 1999, https://doi.org/10.1016/s0022-4073(98)00098-3) in the E‐region of the terrestrial ionosphere. We compare AURIC model outputs using new high‐resolution photoionization and photoabsorption cross sections, and solar spectral irradiances during low solar activity with incoherent scatter radar (ISR) measurements from the Arecibo and Millstone Hills observatories, Constellation Observing System for Meteorology Ionosphere and Climate (COSMIC‐1) observations, and outputs from empirical models (IRI‐2016 and FIRI‐2018). AURIC results utilizing the new high‐resolution cross sections reveal a significant difference to model outputs calculated with the low‐resolution cross sections currently used. Analysis of AURIC EDPs using the new high‐resolution data indicate fair agreement with ISR measurements obtained at various times at Arecibo but very good agreement with Millstone Hills ISR observations from ∼96–140 km. However, discrepancies in the altitude of the E‐region peak persist. High‐resolution AURIC calculations are in agreement with COSMIC‐1 observations and IRI‐2016 model outputs between ∼105 and 140 km while FIRI‐2018 outputs underestimate the EDP in this region. Overall, AURIC modeling shows increased E‐region electron densities when utilizing high‐resolution cross sections and high‐resolution solar irradiances, and are likely to be the key to resolving the long standing data‐model discrepancies.

PANDORA Project for the study of photonuclear reactions below A=60

Photonuclear reactions of light nuclei below a mass of A=60 are planned to be studied experimentally and theoretically with the PANDORA (Photo-Absorption of Nuclei and Decay Observation for Reactions in Astrophysics) project. Two experimental methods, virtual photon excitation by proton scattering and real photo absorption by a high-brilliance gamma -ray beam produced by laser Compton scattering, will be applied to measure the photoabsorption cross sections and decay branching ratio of each decay channel as a function of the photon energy. Several nuclear models, e.g. anti-symmetrized molecular dynamics, mean-field and beyond-mean-field models, a large-scale shell model, and ab initio models, will be employed to predict the photonuclear reactions. The uncertainty in the model predictions will be evaluated based on the discrepancies between the model predictions and experimental data. The data and predictions will be implemented in the general reaction calculation code, TALYS. The results will be applied to the simulation of the photo-disintegration process of ultra-high-energy cosmic rays in inter-galactic propagation.