Photoionization Cross Sections Research Articles

Operation of Photoeelectron Spectrometers for Non-Invasive Photon Diagnostics at the European X-Ray Free Electron Laser

Angle-resolved photoelectron spectrometers with microchannel plate detectors and fast digitizer electronics are versatile and powerful devices for providing non-invasive single-shot photon diagnostics at a MHz repetition rate X-ray free-electron lasers. In this contribution, we demonstrate and characterize the performance of our two operational photoelectron spectrometers for the application of hard X-rays and soft X-rays as well as new automation tools and online data analysis that enable continuous support for machine operators and instrument scientists. Customized software has been developed for the real-time monitoring of photon beam polarization and spectral distribution both in single-color and two-color operation. Hard X-ray operation imposes specific design challenges due to poor photoionization cross-sections and very high photoelectron velocities. Furthermore, recent advancements in machine learning enable resolution enhancement by training the photoelectron spectrometer together with an invasive high-resolution spectrometer, which generates a response function model.

Interatomic Coulombic electron capture beyond the virtual photon approximation.

Via the interatomic Coulombic electron capture (ICEC) process, an electron can be captured by an atom or a molecule, while the binding and excess energy is transferred, via a long-range Coulomb interaction, to a neighboring atom or molecule. The transferred energy can be used to ionize or electronically excite the neighboring species. When the two species are asymptotically far apart, an analytical formula for the ICEC cross sections can be derived. The latter can then be estimated using only the energies and the photoionization cross sections of each species. In this work, we develop an analytical model that allows us to predict the ICEC cross sections when the size of the involved species is comparable to the distance between the two entities. Using abinitio R-matrix results for various systems, we show that the new model reduces the error of the asymptotic formula by two orders of magnitude on average while only using parameters that can be taken from the properties of each species.

Spectral reconstruction for radiation hydrodynamic simulations of galaxy evolution

Radiation from stars and active galactic nuclei (AGN) plays an important role in galaxy formation and evolution, and profoundly transforms the intergalactic, circumgalactic, and interstellar medium (IGM, CGM, and ISM). On-the-fly radiative transfer (RT) has started being incorporated in cosmological simulations, but the complex evolving radiation spectra are often crudely approximated with a small number of broad bands with piece-wise constant intensity and a fixed photo-ionisation cross-section. Such a treatment is unable to capture the changes to the spectrum as light is absorbed while it propagates through a medium with non-zero opacity. This can lead to large errors in photo-ionisation and heating rates. In this work we present a novel approach of discretising the radiation field at discrete photon energies, at the edges of the typically used photo-ionising bands, in order to capture the power-law slope of the radiation field. In combination with power-law approximations for the photo-ionisation cross-sections, this model allows us to self-consistently combine radiation from sources with different spectra and accurately follow the ionisation states of primordial and metal species through time. The method is implemented in GASOLINE2 in connection with TREVR2, a fast reverse ray tracing algorithm with 𝒪(Nactive log2 N) scaling. We compare our new piece-wise power-law reconstruction to the piece-wise constant method in calculating the primordial chemistry photo-ionisation and heating rates under an evolving UV background (UVB) and stellar spectrum, and find that our method reduces errors significantly, by up to two orders of magnitude in the case of HeII ionisation. We apply our new spectral reconstruction method in RT post-processing of a cosmological zoom-in simulation, MUGS2 g1536, including radiation from stars and a live UVB, and find a significant increase in total neutral hydrogen (HI) mass in the ISM and the CGM due to shielding of the UVB and a low escape fraction of the stellar radiation. This demonstrates the importance of RT and an accurate spectral approximation in simulating the CGM-galaxy ecosystem.

On a Study of Photoionization of Atoms and Ions from Endohedral Anions

We study the relationship between the results of two qualitatively different semi-empirical models for photoionization cross sections, σnℓ, of neutral atoms (A) and their cations (A+) centrally encapsulated inside a fullerene anion, CNq, where q represents the negative excess charge on the shell. One of the semi-empirical models, broadly employed in previous studies, assumes a uniform excess negative charge distribution over the entire fullerene cage, by analogy with a charged metallic sphere. The other model, presented here, considers the quantum states of the excess electrons on the shell, determined by specific n and ℓ values of their quantum numbers. Remarkably, both models yield similar photoionization cross sections for the encapsulated species. Consequently, we find that the photoionization of the encapsulated atoms or cations inside the CNq anion is influenced only slightly by the quantum states of the excess electrons on the fullerene cage. Furthermore, we demonstrate that the influence decreases even further as the size of the fullerene cage increases. All this holds true at least under the assumption that the encapsulated atom or cation is compact, i.e., its electron density remains primarily within itself rather than being drawn into the fullerene shell. This remarkable finding results from Hartree–Fock calculations combined with a popular modeling of the fullerene shell which is simulated by an attractive spherical annular potential.

Relativistic calculations of photoionization cross-section of Mg-like Ca IX

Relativistic calculations of photoionization cross-section of Mg-like Ca IX

Examining the influence of electric field on the photoionization cross section and spin polaronic shift in a semimagnetic double quantum well

In the current research, we performed a numerical investigation of a shallow donor impurity confined in a diluted magnetic semiconductor (DMS) double quantum well (DQW) made of a Cd1−xwMnxwTe/Cd1−xbMnxbTe under the applied electric field in the z-direction. The optoelectronic properties were carried out using the effective-mass approximation and the variational method. The binding energy and photoionization cross section were examined by considering different factors such as, well width, barrier width, impurity position, and Manganese mole fraction. Additionally, the spin polaronic shift corrections to the donor binding energy, caused by the strong exchange interaction between the magnetic moment of the Mn2+ the confined carrier spin, have been examined under the aforementioned effects.

Experimental determination of the sulfur K-shell fundamental parameters employing the holistic approach

Abstract Sulfur and its compounds are both very abundant in the environment and very important for technological applications such as batteries. X-ray spectroscopic characterizations of sulfur compounds for a quantitative determination of the present amount of sulfur often requires a good knowledge on the atomic fundamental parameters involved. These quantitatively describe the processes of photoionization and X-ray fluorescence emission, making them crucial for X-ray spectroscopy-based quantifications. 
By employing the recently demonstrated holistic approach, the atomic fundamental parameters of the sulfur K-shell were experimentally determined using the radiometrically calibrated instrumentation of the Physikalisch-Technische Bundesanstalt (PTB). The transition probabilities of the main K-shell fluorescence lines, the K-shell fluorescence yield, the K-shell Auger yield, the subshell photoionization cross section and fluorescence production cross section were determined by means of photon energy dependent X-ray fluorescence and transmission measurements on a thin InS coated silicon nitride membrane. The results are also downloadable from Zenodo as plain text.

Similarity of Near-Threshold Energy Dependence of Positronium Formation and Photoionization in Molecules.

High-resolution measurements of the positronium formation cross sections for positron energies from threshold to 10eV are presented for aniline (C_{6}H_{5}NH_{2}), pyridine (C_{5}H_{5}N), and cyclopentane (C_{5}H_{10}). The data reveal that the measured energy dependence of the cross sections on the excess energy in the near-threshold region (1-2eV) is nearly identical to that of the corresponding photoionization cross sections. This similarity occurs despite the difference between the basic threshold laws for processes without and with a Coulomb interaction between the final-state particles. It is proposed here that the near-threshold behavior of these two different ionization processes is governed by the vibrational dynamics of the final-state cation. This is supported by comparison of the data with the calculated spectrum of vibronic intensities for the pyridine cation [Trofimov etal., J. Chem. Phys. 153, 164307 (2020)JCPSA60021-960610.1063/5.0024446].

Stabilization of U 5f2 configuration in UTe2 through U 6d dimers in the presence of Te2 chains

We investigate the topological superconductor candidate UTe2 using high-resolution valence-band resonant inelastic x-ray scattering at the U M4,5 edges. We observe atomiclike low-energy excitations that support the correlated nature of this unconventional superconductor. These excitations originate from the U 5f2 configuration, which is unexpected since the short Te2-Te2 distances exclude Te2 being 2−. By utilizing the photoionization cross-section dependence of the photoemission spectra in combination with band structure calculations, we infer that the stabilization of the U 5f2 configuration is due to the U 6d bonding states in the U dimers acting as a charge reservoir. Our results emphasize that the description of the physical properties should commence with a 5f2 ansatz. Published by the American Physical Society 2024

Intensity-energy response function of Al/Cr-K[formula omitted] x-ray photoemission instruments: An inter-laboratory study

The question of the intensity-energy response of photoemission spectrometers has been approached through a round-robin involving 13 instruments working with low (Al/Mg-Kα) and high (Cr-Kα) energy photon sources. An algorithm based on the analysis of inelastic background previously proposed [S. Guilet et al., J. Electron Spectrosc. Relat. Phenom. 285 (2022) 147225)] was intensively tested against calibrated Al/Mg-Kα instruments and calculated relative sensitivity factors (RSFs) over the 15 core level peaks of coinage metals (Ag, Au, Cu). In both cases, the linear correlation within ±10 %, over two orders of magnitude in intensity and for kinetic energies ranging from ∼400 to 1400eV, showed the consistency of the approach. All the contributions to RSFs (e.g. non-dipolar terms in the photo-ionization cross section, elastic scattering effects, surface excitations, beam polarization by the monochromator) were critically reviewed and taken into account using the state-of-the-art modellings and databases. Strong variations were evidenced among instruments, regarding not only the response functions, but also the theoretical RSFs due to different measurement geometries. For the Cr-Kα hard x-ray instruments, the same analysis was performed with a set of different materials (Al, Si, Ge, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ag, W, Au). A ±10 % satisfactory agreement against theoretical RSFs over 69 core levels spanning a large kinetic energy range (300–4000 eV) could be achieved with a common response function. Despite limitations that are reviewed, this work opens interesting perspectives for a systematic calibration of photoemission instruments.

Relation between photoionisation cross sections and attosecond time delays

Abstract Determination and interpretation of Wigner-like photoionisation delays is one of the most active fields of attosecond science. Previous results have suggested that large photoionisation delays are associated with structured continua, but a quantitative relation between photoionisation cross sections and time delays has been missing. Here, we derive a Kramers-Kronig-like relation between these quantities and demonstrate its validity for (anti)resonances. This new concept defines a topological analysis, which rationalises the sign of photoionisation delays and thereby sheds new light on a long-standing controversy regarding the sign of the photoionisation delay near the Ar 3s Cooper minimum. Our work bridges traditional photoionisation spectroscopy with attosecond chronoscopy and offers new methods for analysing and interpreting photoionisation delays.

An experimental study of surrogates of diesel from indirect coal liquefaction and the development of an improved kinetic mechanism

The increasing energy shortage and environmental pollution make the use of clean and efficient alternative fuels an effective way to solve the emission problem. Diesel from indirect coal liquefied (DICL) is a clean and efficient alternative fuel for diesel engines. The composition and chemical kinetics mechanism of DICL research contributes to a better understanding of combustion and pollutant formation process. The components of DICL were analysed by gas chromatography-mass spectrometry (GC-MS). The proportion of normal alkanes contained in DICL is particularly high, 93.82%, which proves that its reactivity is particularly good. The mixture of n-dodecane and iso-octane was selected as the surrogates of DICL. The oxidation process of DICL surrogates was examined by a jet-stirred reactor (JSR) over the temperature range of 500–890 K. A detailed kinetic mechanism of surrogates encompassing 1356 species and 6008 reactions was constructed. The critical reactions associated with the reactivity of surrogates were adjusted by the sensitivity analysis method to increase the accuracy of mechanism prediction. The predicted value of the improved mechanism is in good agreement with the experimental value. The improved mechanism can reasonably predict the oxidation process and the ignition characteristics of DICL and the improved mechanism can provide a good reference value for the subsequent analysis of combustion and emission problems of DICL. Abbreviations: C/H, C/H ratio; CN, cetane number; DDCL, direct coal liquefy diesel; DICL, Diesel from indirect coal liquefied; GC-MS, gas chromatography-mass spectrometry; HMN, 2,2,4,4,6,8,8-heptamethylnonane; HXN, n-hexadecane; IDT, ignition delay time; JSR, jet-stirred reactor; LHV, low heating value; LLNL, Lawrence Livermore National Laboratory; NSRL, National Synchrotron Radiation Laboratory; NTC, negative temperature coefficient; PICS, photoionization cross section; PRF, gasoline substitute; PSR, perfectly stirred reactor; SVUV-PIMS, Synchrotron VUV photoionization mass spectrometry; TOF-MS, time-of-flight mass spectrometer

Photoionization of hydrogen halides using the R-matrix method

Abstract In this study, we use the UK Molecular R-matrix (UKRMol) codes in the close-coupling approximation to examine the photoionization of hydrogen halides (hydrogen fluoride, hydrogen chloride, and hydrogen bromide). This article reports the total and partial photoionization cross sections for the X2Π, A2Σ+, and B2Σ+ ionic states of these halides. The calculated cross sections are compared with the available literature, which does not accurately represent the effective cross sections near the threshold region, which is dominated by the Rydberg series autoionization resonances converging to the A2Σ+ ionic state. There seems to have been minimal effort to investigate the Rydberg-bound states of these halides. Meanwhile, the R-matrix approaches have traditionally excelled at characterizing such studies. This indicates the effectiveness of this method for molecular photoionization as well as for understanding the resonant contribution to the photoionization cross sections. The detailed cross sections calculated comprise the complex autoionizing resonance structures capable of significantly contributing to the computations of total photoionization rates, which are necessary to maintain a steady state of ionization in astrophysical plasmas. Comparisons with the experimental measurements and the theoretical data generally show reasonable agreement across the reported energy range.

The combined effects of electric field and embedded dielectric matrix on the electronic and optical properties in Ge/SiGe core/shell quantum dots and its SiGe/Ge inverted structure

In this study, the binding energy (BE) and photoionization cross-section (PICS) coefficients in a Ge/Si0.15Ge 0.85 core/shell quantum dots (CSQDs) and in its inverted structure Si0.15Ge0.85 / Ge (ICSQDs) are studied. The influence of the hydrogenic impurity and capped matrix are taken into account. The electronic states and their related eigenfunctions are computed by solving the three-dimensional Schrödinger equation under the framework of the effective mass approximation (E.M.A) using the variational dimensional. The influence of the core radius and electric field strength on the BE and PICS are investigated. The numerical results reveal that the optoelectronic properties are considerably affected by the electric field strength (EF), immersed oxide matrix (OM) and geometric parameter. The obtained results prove that the PICS magnitude increases as the core radius increases and its resonant peak moves towards the lower energies for Ge/Si0.15Ge0.85 CSQDs structure, and increases as the core radius decreases and its resonant peak experiences a blue shift with increasing core radius for Si0.15Ge 0.85/ Ge ICSQDs. Moreover, with the effects of the surrounding oxide matrix and electric field strength, the PICS magnitude is improved and their resonant peak suffers a redshift.

Rotating effects on the photoionization cross-section of a 2D quantum ring

In this article, we investigate the nonrelativistic quantum motion of a charged particle within a rotating frame, taking into account the Aharonov–Bohm (AB) effect and a uniform magnetic field. Our analysis entails the derivation of the equation of motion and the corresponding radial equation to describe the system. Solving the resulting radial equation enables us to determine the eigenvalues and eigenfunctions, providing a clear expression for the energy levels. Furthermore, our numerical analysis highlights the substantial influence of rotation on both energy levels and optical properties. Specifically, we evaluate the photoionization cross-section with and without the effects of rotation. To elucidate the impact of rotation on the photoionization process of the system, we present graphics that offer an appealing visualization of the intrinsic nature of the physics involved.

Thermal decomposition study of 1,3-dioxolane as a representative of battery solvent

As industrial compounds and organic solvent, 1,3-dioxolane (C3H6O2) is used in lithium-ion batteries arousing extensive interest. The pyrolysis of C3H6O2 at 150 torr pressure was conducted in the temperature range of 743–1013 K. In order to quantify the major products, experimental measurements of the photoionization cross-section (PICS) and photoionization efficiency (PIE) for C3H6O2 were carried out by using synchrotron radiation photoionization mass spectrometry (SR-PIMS). Twenty-three intermediates were detected in pyrolysis of C3H6O2 including the newly observed ketene, acetaldehyde, ethenol, ethanol, dimethyl ether, diacetylene and 2-propen-1-ol which played important roles in developing mechanism. The H-abstraction of C3H6O2 by H, CH3 and OH radicals were studied via high level ab initio calculations. EStokTP code was used to find and calculate optimal geometries, vibration frequencies and intrinsic reaction coordinate (IRC) at the theory level of M06–2X/6–311+G(d,p). Conventional transition state theory (TST) was used and Rice-Ramsperger-Kassel-Marcus/Master Equation (RRKM/ME) was solved to obtain rate coefficients. For H-abstraction by H and CH3, the rates are increasing versus temperature, and rates of H-abstraction by OH show different tendency. These rate parameters were used to update the model of C3H6O2, which could well predict the ignition delay times (IDTs) in shock tube and oxidation data in jet stirred reactor (JSR) from literature. For the pyrolysis, H-abstraction reactions by H, CH3 and OH and unimolecular reactions contribute to solvent decay. Detailed pathways of C3H6O2 decomposition were also given and analyzed through this experiment and previous literature. The findings, including the experimental data and the calculations will assist to better understand pyrolysis characteristics of C3H6O2 as well.

Further investigation of spatially resolved single grain quartz OSL and TL signals

The use of luminescence signals from single mineral grains for optical dating has become a valuable and frequently utilised tool in Quaternary Geochronology. Single grain luminescence dating is particularly beneficial in complex depositional settings, however the ability to measure single grain signals also offers the opportunity to assess intrinsic luminescence properties of individual mineral grains. The use of spatially resolved luminescence technologies such as an electron multiplier charge coupled device is of benefit when making luminescence measurements at single grain scales because they allow stimulation with light emitting diodes, and this offers a number of key benefits related to stimulation power when it comes to the assessment of characteristics such as optically stimulated luminescence (OSL) decay rate and the calculation of parameters such as the fast ratio and photo ionisation cross-sections. In this paper, the intra- and inter-sample variability of sensitised single grain thermoluminescence (TL) and OSL signals is considered. A comparison between TL and OSL signals is undertaken, as well as calculation of the fast ratio, OSL component photo ionisation cross-sections, thermal stability, and characteristic dose for a suite of quartz samples from a range of geographic locations and depositional settings. For these heated signals, key findings include the lack of relationship between OSL signal intensity and dominance of the fast component, the fitting of two components (a fast and slow component) is the most common fit for single grain OSL signals, characteristic doses from fast dominated signals suggesting saturation at c. 150 Gy, and the identification of the ultrafast OSL component. Intra-sample variability across all measured parameters is observed, suggesting that for this suite of samples, variability is the norm rather than the exception, and that the intrinsic luminescence characteristics of quartz are variable and diverse.

Quantifying the U 5f covalence and degree of localization in U intermetallics

A procedure for quantifying the U 5f electronic covalency and degree of localization in U intermetallic compounds is presented. To this end, bulk sensitive hard and soft x-ray photoelectron spectroscopy were utilized in combination with density-functional theory (DFT) plus dynamical mean-field theory (DMFT) calculations. The energy dependence of the photoionization cross sections allows the disentanglement of the U 5f contribution to the valence band from the various other atomic subshells so the computational parameters in the DFT+DMFT can be reliably determined. Applying this method to UGa2 and UB2 as model compounds from opposite ends of the (de)localization range, we have achieved excellent simulations of the valence band and core-level spectra. The width in the distribution of atomic U 5f configurations contributing to the ground state, as obtained from the calculations, quantifies the correlated nature and degree of localization of the U 5f. The findings permit answering the longstanding question why different spectroscopic techniques give seemingly different numbers for the U 5f valence in intermetallic U compounds. Published by the American Physical Society 2024

Continuum spectrum of atomic lithium in a magnetic field of white dwarfs

ABSTRACT This paper reports on computational results of continuum spectra of atomic lithium in white-dwarf-strength magnetic fields. The adiabatic-basis-expansion method with R-matrix propagation has been used to study photoionization of magnetized alkali metal atoms. The R-matrix propagation technique and the two-dimensional matching scheme were utilized to obtain wavefunctions of the continuum states. Cross-sections of photoionization are calculated for lithium atoms in magnetic fields. Continuum spectra for its various bound-free transitions in magnetic white dwarf stars are presented as a function of field strengths ranging from 11.75 to 117.50 MG. Comparison is made between continuum spectra of diamagnetic hydrogen and lithium atoms. The comparison shows good agreement or remarkable difference for final continuum states with different symmetries in the photoionization processes concerned. A detailed analysis has been performed to understand the obtained results. The good agreement displayed manifests the reliability of the extended adiabatic-basis-expansion method. This method is suited to produce a large number of photoionization cross-section data for alkali metal atoms in a strong magnetic field, and therefore can serve as a tool to simulate continuum spectra observed in the atmospheres of magnetic white dwarfs with alkali metal atoms.

Two-photon laser-induced fluorescence study of the CO B 1Σ+ (v' = 0) state in a 4850K plasma plume: Modified molecular constants, evidence of predissociation, and J'-dependent photoionization.

We report the two-photon absorption laser-induced fluorescence rotational spectrum of the CO B 1Σ+ ← X 1Σ+ Hopfield-Birge system (v' = 0, v″ = 0) Q-branch in an ∼4850K, atmospheric pressure plasma torch plume at thermal equilibrium in both the quenching-dominated (low laser intensity) and photoionization-dominated (high laser intensity) regimes. We provide a detailed analysis of the photophysics in these two regimes using a rate equation approach and propose modeling considerations for them as well. In the experimental spectra, distinct rotational transitions up to J″ = 83 are observed, allowing analysis over a very large range of rotational states. Evidence of predissociation is observed for J' ≥ 64 and is likely due to the interaction with the D'1Σ+ electronic state, which has been proposed in the literature but never observed in the v' = 0 state. The line positions of higher rotational states show disagreement with line positions calculated from molecular constants in the available literature, suggesting the need for modifications to the constants, which are reported here. A shift in the B 1Σ+ ← X 1Σ+ absorption spectrum toward higher two-photon energy as a result of the second-order Stark shift was observed in the photoionization-dominated spectrum, and the second-order Stark shift cross section was estimated to be 7 ± 3 × 10-18 cm2. The mean photoionization cross section of the excited upper state was inferred by comparing the line broadening of the two spectra and was estimated to be 11 ± 7 × 10-18 cm2. In addition, weak J'-dependent variations of the photoionization cross section were observed and are reported here.