Direct Photoionization Research Articles

Generation of ultrashort ion pulses from ultrafast electron-stimulated desorption

We present an efficient method to produce laser-triggered proton pulses well below 500 ps pulse width at keV energies. We use femtosecond photoelectron pulses emitted from a cathode to enable ultrafast electron-stimulated desorption of adsorbates on a stainless steel plate under ultrahigh vacuum conditions. While direct photoionization of atoms to form well-timed ion pulses can suffer from a laser-focus-limited large starting volume, in our method the two-dimensional starting plane of the ions is defined with nanometer precision at a solid surface. We clearly outline how the method could be used in the future to efficiently produce ion beam pulses in the (sub)picosecond range for pump-probe experiments with ions. Published by the American Physical Society 2024

X-ray radiation damage cycle of solvated inorganic ions

X-ray-induced damage is one of the key topics in radiation chemistry. Substantial damage is attributed to low-energy electrons and radicals emerging from direct inner-shell photoionization or produced by subsequent processes. We apply multi-electron coincidence spectroscopy to X-ray-irradiated aqueous solutions of inorganic ions to investigate the production of low-energy electrons (LEEs) in a predicted cascade of intermolecular charge- and energy-transfer processes, namely electron-transfer-mediated decay (ETMD) and interatomic/intermolecular Coulombic decay (ICD). An advanced coincidence technique allows us to identify several LEE-producing steps during the decay of 1s vacancies in solvated Mg2+ ions, which escaped observation in previous non-coincident experiments. We provide strong evidence for the predicted recovering of the ion’s initial state. In natural environments the recovering of the ion’s initial state is expected to cause inorganic ions to be radiation-damage hot spots, repeatedly producing destructive particles under continuous irradiation.

Pre-supernova stellar feedback in nearby starburst dwarf galaxies

Stellar feedback in dwarf galaxies remains, to date, poorly explored, yet is crucial to understanding galaxy evolution in the early Universe. In particular, pre-supernova feedback has recently been found to play a significant role in regulating and disrupting star formation in larger spiral galaxies, but it remains uncertain if it also plays this role in dwarfs. We study the ionised gas properties and stellar content of individual star-forming regions across three nearby, low-metallicity ($12+ O/H 7.5$), dwarf ($M_* odot $), starburst ($ SFR -2.8$) galaxies (J0921, KKH046, and Leo P) to investigate how massive stars influence their surroundings and how this influence changes as a function of environment. We extracted integrated spectra of 30 HII regions from archival VLT/MUSE integral field spectroscopic observations of these three dwarf starburst galaxies. We fitted the HII regions' main emission lines with Gaussian profiles to derive their oxygen abundances, electron densities, and luminosities, and we used the Stochastically Ligthing Up Galaxies ( SLUG ) code to derive the stellar mass, age, and bolometric luminosity of the stellar populations driving the HII regions. We quantified two pre-supernova stellar feedback mechanisms, namely the direct radiation pressure and photoionisation feedback, and explored how feedback strength varies with HII region properties. Our findings suggest that stellar feedback has less of an impact on evolved regions, with both the pressure of the ionised gas and the direct radiation pressure decreasing as a function of HII region size (i.e. the evolutionary stage). We find that these stellar feedback mechanisms are also dependent on the metallicity of the HII regions. These findings extend results from stellar feedback studies of more massive star-forming galaxies to the low-mass, low-metallicity regime. In addition, we conclude that the use of stochastic stellar population models significantly affects the relationships found between feedback-related pressure terms and HII region properties, and in particular that non-stochastic models can severely underestimate the bolometric luminosity of low-mass stellar populations.

A multiphoton ionisation photoelectron imaging study of thiophene.

Thiophene is a prototype for the excited state photophysics that lies at the heart of many technologies within the field of organic electronics. Here, we report a multiphoton ionisation photoelectron imaging study of gas-phase thiophene using a range of photon energies to excite transitions from the ground electronic state to the first two electronically excited singlet states, from the onset of absorption to the absorption maximum. Analysis of the photoelectron spectra and angular distributions reveal features arising from direct photoionisation from the ground electronic state, and resonance-enhanced photoionisation via the electronically excited singlet states. The first two ionisation energies from the ground electronic state were confirmed to be 8.8 eV (adiabatic) and 9.6 eV (vertical). The ionisation energies from the first two electronically excited singlet states were found to be 3.7 eV (adiabatic) and 4.4 eV (vertical).

Can methylated purine bases act as photoionization hotspots?

The direct photoionization of DNA canonical bases under ultraviolet radiation is difficult due to the high ionization potentials. According to previous quantum chemical calculations, methylation can have great influence on the ionization potential. Are methylated nucleobases prone to photoionization and cause DNA damage? As an important epigenetic modification in transcription, expression, and regulation of genes, it is of great biological significance to explore the effect of methylation on base photoionization from the experimental perspective. Herein, we study the photoionization behavior of methylated purines 6 mA and 6mG at 266 nm using a nanosecond transient UV-Vis spectroscopy. The hydrated electron and methylated base radicals are observed, indicating the occurrence of photoionization for both 6mG and 6 mA. We measured one-photon ionization yields to be (5.0 ± 0.2) × 10-3 and (1.4 ± 0.2) × 10-3 for 6mG and 6 mA, respectively. These are higher than those of (dA)20 and (dA20 )·(dT20 ) previously reported, indicating that methylation significantly promotes base photoionization with a stronger effect than base stacking, consistent with calculations in literature. Given that the hydrated electrons and methylated base radicals from photoionization can trigger a cascade of deleterious reactions, the methylated purine bases may act as hotspots of DNA photoionization damage of living organisms.

The Role of Stepwise Photoionization in Measurements of the Ionization Potentials in Dense Plasma

The interaction of high-contrast high-intensity laser radiation with solids allows us to create hot or warm plasma of solid or even over-solid density, such as in the case of inertial fusion particularly. The multicharged ions contained in it can no longer be considered isolated. As a result, this leads to a decrease in the ionization potentials and to the disappearance of a number of bound ionic states. To describe the ionization potential depression, two major approaches are now used predominantly, where the key parameter is either average interelectronic or interionic distance. Since neither of the approaches can be substantiated purely theoretically, their applicability can only be established by comparison with experimental results. In recent experiments with X-ray free-electron lasers, it was concluded that the ionization potential depression rather depends on the interelectronic distance. However, when measuring ionization potentials, it was assumed that the main role in ionization processes is played by the direct photoionization of the ion ground state. In the present paper, we show that stepwise photoionization processes should play a significant role in dense plasma, disrupting a straight correspondence between the threshold in direct photoionization by X-ray laser photons and the actual ionization potential of multicharged ions. It means that the measurement results mentioned above are not correct, and the main conclusion about the importance of the interelectronic distance for depression of the ionization potential is not correct.

Detailed Comparison of Xenon APPI (9.6/8.4 eV), Krypton APPI (10.6/10.0 eV), APCI, and APLI (266 nm) for Gas Chromatography High Resolution Mass Spectrometry of Standards and Complex Mixtures.

Photoionization schemes for mass spectrometry, either by laser or discharge lamps, have been widely examined and deployed. In this work, the ionization characteristics of a xenon discharge lamp (Xe-APPI, 9.6/8.4 eV) have been studied and compared to established ionization schemes, such as atmospheric pressure chemical ionization, atmospheric pressure photoionization with a krypton discharge lamp (Kr-APPI, 10.6/10 eV) and atmospheric pressure laser ionization (266 nm). Addressing the gas-phase ionization behavior has been realized by gas chromatography coupled to high-resolution mass spectrometry without the usage of a dopant. For standard substances, it has been found that Xe-APPI is able to ionize a broad range of polycyclic aromatic hydrocarbons as well as their heteroatom-containing and alkylated derivatives. However, thiol and ester compounds could not be detected. Moreover, Xe-APPI revealed a high tendency to generate oxygenated artifacts, most likely due to a VUV absorption band of oxygen at 148 nm. Beneficially, almost no chemical background, commonly caused by APCI or Kr-APPI due to column blood, plasticizers or impurities, is observed. This advantage is noteworthy for evolved gas analysis without preseparation or for chromatographic coelution. For the complex mixtures, Xe-APPI revealed the predominant generation of radical cations via direct photoionization with a high selectivity toward aromatic core structures with low alkylation. Interestingly, both Xe-APPI and Kr-APPI could sensitively detect sterane cycloalkanes, validated by gas chromatographic retention. The narrowly ionized chemical space could let Xe-APPI find niche applications, e.g., for strongly contaminated samples to reduce the background.

Autoionization from the plasmon resonance in isolated 1-cyanonaphthalene.

Polycyclic aromatic hydrocarbons have widely been conjectured to be ubiquitous in space, as supported by the recent discovery of two isomers of cyanonaphthalene, indene, and 2-cyanoindene in the Taurus molecular cloud-1 using radioastronomy. Here, the photoionization dynamics of 1-cyanonaphthalene (1-CNN) are investigated using synchrotron radiation over the hν = 9.0-19.5eV range, revealing that prompt autoionization from the plasmon resonance dominates the photophysics for hν = 11.5-16.0eV. Minimal photo-induced dissociation, whether originating from an excited state impulsive bond rupture or through internal conversion followed by a statistical bond cleavage process, occurs over the microsecond timescale (as limited by the experimental setup). The direct photoionization cross section and photoelectron angular distributions are simulated using an ezDyson model combining Dyson orbitals with Coulomb wave photoejection. When considering these data in conjunction with recent radiative cooling measurements on 1-CNN+, which showed that cations formed with up to 5eV of internal energy efficiently stabilize through recurrent fluorescence, we conclude that the organic backbone of 1-CNN is resilient to photodestruction by VUV and soft XUV radiation. These dynamics may prove to be a common feature for the survival of small polycyclic aromatic hydrocarbons in space, provided that the cations have a suitable electronic structure to support recurrent fluorescence.

The resolved chemical composition of the starburst dwarf galaxy CGCG007-025: direct method versus photoionization model fitting

ABSTRACTThis work focuses on the gas chemical composition of CGCG007-025. This compact dwarf is undergoing a galaxy wide star-forming burst, whose spatial behaviour has been observed by VLT/MUSE. We present a new line measurement library to treat almost 7800 voxels. The direct method chemical analysis is limited to 484 voxels with good detection of the $[\mathrm{S}\, {\small III}]6312\, \mathring{\rm A}$ temperature diagnostic line. The recombination fluxes are corrected for stellar absorption via a population synthesis. Additionally, we discuss a new algorithm to fit photoionization models via neural networks. The eight ionic abundances analysed show a spatial normal distribution with a $\sigma \sim 0.1\, {\rm dex}$, where only half this value can be explained by the uncertainty in the measurements. The oxygen abundance distribution is 12 + log(O/H) = 7.88 ± 0.11. The ${\it T}_{e}[\mathrm{S}\, {\small III}]$ and ne[S ii] are also normally distributed. However, in the central and brightest region, the ne[S ii] is almost thrice the mean galaxy value. This is also reflected in the extinction measurements. The ionization parameter has a distribution of ${\rm log}(U) = -2.52^{0.17}_{0.19}$. The parameter spatial behaviour agrees with the S2+/S+ map. Finally, the discrepancies between the direct method and the photoionization model fitting are discussed. In the latter technique, we find that mixing lines with uneven uncertainty magnitudes can impact the accuracy of the results. In these fittings, we recommend overestimating the minimum flux uncertainty one order below the maximum line flux uncertainty. This provides a better match with the direct method.

Nanoliter atmospheric pressure photoionization-mass spectrometry for direct bioanalysis of polycyclic aromatic hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) are a class of low-polarity environmental contaminants that have severe carcinogenic effects and have drawn worldwide attention. However, there remain challenges for current mass spectrometric ionization techniques in the analysis of low-polarity compounds in small-volume biosamples, such as single cells. In this work, we developed a nanoliter atmospheric pressure photoionization (nano-APPI) source and optimized its parameters for the detection of PAHs in small-volume samples. We evaluated the ionization performance of the source in direct and auxiliary gas-assisted photoionization modes and analyzed different PAH compounds as well as spiked biosamples. By combining the advantages of nano-electrospray ionization (nano-ESI) and atmospheric pressure photoionization (APPI), our newly developed nano-APPI source achieved high sensitivity for the analysis of PAHs down to the fmol level. Compared to conventional atmospheric pressure chemical ionization (APCI), the detection limit of PAHs was increased by 1-2 orders of magnitude. By optimizing various parameters, we achieved highly efficient ionization of PAHs, effective analysis of PAHs in mixed components, and sensitive detection of low-abundance PAHs in single-cell samples. Our optimized nano-APPI source was successfully applied for the sensitive analysis of PAHs in complex biological samples. Based on our study, we believe that nano-APPI holds great promise for toxicological studies on complex biological samples. The present work has implications for improving the detection sensitivity of low-polarity environmental contaminants and advancing the field of MS-based analysis of small-volume biosamples.

Secondary ionization of pyrimidine nucleobases and their microhydrated derivatives in helium nanodroplets.

Radiation damage in biological systems by ionizing radiation is predominantly caused by secondary processes such as charge and energy transfer leading to the breaking of bonds in DNA. Here, we study the fragmentation of cytosine (Cyt) and thymine (Thy) molecules, clusters and microhydrated derivatives induced by direct and indirect ionization initiated by extreme-ultraviolet (XUV) irradiation. Photofragmentation mass spectra and photoelectron spectra of free Cyt and Thy molecules are compared with mass and electron spectra of Cyt/Thy clusters and microhydrated Cyt/Thy molecules formed by aggregation in superfluid helium (He) nanodroplets. Penning ionization after resonant excitation of the He droplets is generally found to cause less fragmentation compared to direct photoionization and charge-transfer ionization after photoionization of the He droplets. When Cyt/Thy molecules and oligomers are complexed with water molecules, their fragmentation is efficiently suppressed. However, a similar suppression of fragmentation is observed when homogeneous Cyt/Thy clusters are formed in He nanodroplets, indicating a general trend. Penning ionization electron spectra (PIES) of Cyt/Thy are broad and nearly featureless but PIES of their microhydrated derivatives point at a sequential ionization process ending in unfragmented microsolvated Cyt/Thy cations.

Relevance of dissociative molecular states for resonant two-center photoionization of heteroatomic dimers

Photoionization of a weakly bound van-der-Waals dimer, composed of two atomic species A and B, is studied theoretically. Atom A can be ionized either directly or via an indirect two-center channel, where atom B is first resonantly photoexcited and, afterwards, transfers the excitation energy via long-range electron–electron correlations radiationlessly to atom A, causing its ionization. By taking the vibrational nuclear motion of the dimer during the process into account, we analyze the contributions to the photoionization cross section from bound and dissociative molecular states in the final –B system. For the specific example of a LiHe dimer we show (a) that substantial contributions to both ionization mechanisms result from dissociative Li He states and (b) that the two-center pathway strongly dominates over the direct photoionization channel for photon energies close to one of the molecular LiHe resonances.

Low Energy Photoionization of Phosphorothioate DNA-Oligomers and Ensuing Hole Transfer.

Phosphorothioate (PS) modified oligonucleotides (S-DNA) naturally exist in bacteria and archaea genome and are widely used as an antisense strategy in gene therapy. However, the introduction of PS as a redox active site may trigger distinct UV photoreactions. Herein, by time-resolved spectroscopy, we observe that 266 nm excitation of S-DNA d(Aps)20 and d(ApsA)10 leads to direct photoionization on the PS moiety to form hemi-bonded -P-S∴S-P- radicals, in addition to A base ionization to produce A+•/A(-H)•. Fluorescence spectroscopy and global analysis indicate that an unusual charge transfer state (CT) between the A and PS moiety might populate in competition with the common CT state among bases as key intermediate states responsible for S-DNA photoionization. Significantly, the photoionization bifurcating to PS and A moieties of S-DNA is discovered, suggesting that the PS moiety could capture the oxidized site and protect the remaining base against ionization lesion, shedding light on the understanding of its existence in living organisms.

Electronic state influence on selective bond breaking of core-excited nitrosyl chloride (ClNO).

The potential for selective bond breaking of a small molecule was investigated with electron spectroscopy and electron-ion coincidence experiments on ClNO. The electron spectra were measured upon direct valence photoionization and resonant core excitation at the N 1s- and O 1s-edges, followed by the emission of resonant-Auger (RA) electrons. The RA spectra were analyzed with particular emphasis on the assignment of the participator and spectator states. The states are of special relevance for investigating how distinct electronic configurations influence selective bond breaking. The electron-ion coincidence measurements provided branching fractions of the produced ion fragments as a function of electron binding energy. They explicitly demonstrate how the final electronic states created after photoionization and RA decay influence fragmentation. In particular, we observed a significantly different branching fraction for spectator states compared with participator states. In addition, it was also observed that the bonds broken for the spectator states correlate with the antibonding nature of the spectator-electron orbital.

Multiple flares caused by mass ejection episodes during the advanced nebular phase of Nova Scuti 2019

ABSTRACT Our photometric and spectroscopic monitoring shows that starting with 2020 June 4, day +217 from optical maximum and well into its advanced nebular stage, Nova Scuti (Nova Sct) 2019 begun displaying a series of nine large amplitude flares (up to $\Delta m \sim 1.7$ mag), characterized by a rapid rise to peak (≤10 h) and a fast exponential decline (e-folding time ∼50 h). The time interval Δt between flares follows an ordered sequence, declining from 8.43 to 4.90 d, that safely allows to exclude that any other flare occurred without being recorded by the observations. When the sequence of flares was over by 2020 July 28 (day +271), Nova Sct 2019 slowed its overall decline rate from Δm = 0.0067 to 0.0027 mag d−1. The flares were caused by material expelled at high velocity (∼1000 km s−1) from the still burning white dwarf (WD). The cooler pseudo-photosphere forming at each flare in the expelled material, resulted in a recombination wave to spread through the original nova ejecta (at ∼170 au from the WD), quenching emission from [Fe x] and [Fe vii] and boosting that from lower ionization species. After each flare, once the small amount of expelled material had turned optically thin, the original nova ejecta resumed displaying [Fe x] and [Fe vii] emission lines, a fact that clearly proves the direct photoionization action exerted on the ejecta by the burning WD. While the other known flaring novae (V458 Vul, V4745 Sgr, and V5588 Sgr) presented the flares close to maximum brightness and with increasing Δt, Nova Sct 2019 is unique in having displayed them during the advanced nebular stage and with decreasing Δt.

Non-dipole anisotropy parameters in the photoionization of Kr in the region of deep inner shell excitations

The photoelectron angular distribution (PAD) of the Kr 4p1/2 and 4p3/2 fine structure states was measured with linearly polarized synchrotron radiation in the vicinity of the resonant excitations of the 3p subshell. Experimental dipole and non-dipole anisotropy parameters were determined from the measured angular differential cross sections. In order to interpret our experimental results we have used a theoretical model going beyond the dipole approximation considering the quadrupole and octupole terms for the direct photoionization. We have taken into account several autoionization channels relevant for the studied photon energy range. The photon energy dependence of the measured anisotropy parameters puts in evidence the importance of the channel interactions. Moreover, unexpectedly large non-dipole contribution have been observed.

New insights on the nebular emission, ionizing radiation, and low metallicity of Green Peas from advanced modelling

ABSTRACT Low-metallicity, compact starburst galaxies referred to as Green Peas (GPs) provide a unique window to study galactic evolution across cosmic epochs. In this work, we present new deep optical spectra for three GPs from OSIRIS at the 10-m Gran Telescopio Canarias, which are studied using a state-of-the-art methodology. A stellar population synthesis is conducted with 1098 spectral templates. The methodology succeeds at characterizing stellar populations from 0.5 Myr to 10 Gyr. The light distribution shows a large red excess from a single population with ${log}\left({age}\right) \gt 8.5\, \mathrm{yr}$ in the GP sample analysed. This points towards an incomplete characterization of the gas luminosity, whose continuum already accounts between 7.4 and $27.6{{\ \rm per\ cent}}$ in the galaxy sample. The emission spectra are fitted with the largest Bayesian chemical model consisting of an electron temperature, an electron density, the logarithmic extinction coefficient and eleven ionic species under the direct method paradigm. Additionally, building on previous work, we propose a neural networks sampler to constrain the effective temperature and ionization parameter of each source from photoionization model grids. Finally, we combine both methodologies into a 16-dimensional model, which for the first time, simultaneously explores the direct method and photoionization parameter spaces. Both techniques consistently indicate a low-metallicity gas, $7.76\lt 12+{\rm log}\left(O/H \right)\lt 8.04$, ionized by strong radiation fields, in agreement with previous works.

Experimental and Computational Studies on the Reactivity of Methanimine Radical Cation (H2CNH+•) and its Isomer Aminomethylene (HCNH2+•) With C2H2

Experimental and theoretical studies are presented on the reactivity of the radical cation isomers H2CNH+• (methanimine) and HCNH2+• (aminomethylene) with ethyne (C2H2). Selective isomer generation is performed via dissociative photoionization of suitable neutral precursors as well as via direct photoionization of methanimine. Reactive cross sections (in absolute scales) and product branching ratios are measured as a function of photon and collision energies. Differences between isomers’ reactivity are discussed in light of ab-initio calculations of reaction mechanisms. The major channels, for both isomers, are due to H atom elimination from covalently bound adducts to give [C3NH4]+. Theoretical calculations show that while for the reaction of HCNH2+• with acetylene any of the three lowest energy [C3NH4]+ isomers can form via barrierless and exothermic pathways, for the H2CNH+• reagent the only barrierless pathway is the one leading to the production of protonated vinyl cyanide (CH2CHCNH+), a prototypical branched nitrile species that has been proposed as a likely intermediate in star forming regions and in the atmosphere of Titan. The astrochemical implications of the results are briefly addressed.

Molecular-Frame Photoelectron Angular Distributions of CO in the Vicinity of Feshbach Resonances: An XCHEM Approach.

The advent of ultrashort XUV pulses is pushing for the development of accurate theoretical calculations to describe ionization of molecules in regions where electron correlation plays a significant role. Here, we present an extension of the XCHEM methodology to evaluate laboratory- and molecular-frame photoelectron angular distributions in the region where Feshbach resonances are expected to appear. The performance of the method is demonstrated in the CO molecule, for which information on Feshbach resonances is very scarce. We show that photoelectron angular distributions are dramatically affected by the presence of resonances, to the point that they can completely reverse the preferred electron emission direction observed in direct nonresonant photoionization. This is the consequence of significant changes in the electronic structure of the molecule when resonances decay, an effect that is mostly driven by electron correlation in the ionization continuum. The present methodology can thus be helpful for the interpretation of angularly resolved photoionization time delays in this and more complex molecules.

Electron attachment to a proton in water by interatomic Coulombic electron capture: An R -matrix study

Interatomic Coulombic electron capture (ICEC) is an environment-enabled electron capture process in which a free electron can efficiently attach to a quantum system by transferring the excess energy to a neighbor thus ionizing it. Using the ab initio $R$-matrix method, we investigate the electron attachment to a proton in the neighborhood of a water molecule. The corresponding ICEC cross sections exhibit clear Fano profiles, resulting from interferences between the ICEC final states and resonant states. These Fano interferences, observed in the total ICEC cross sections, were discussed in our recent work on large system-neighbor separations [A. Molle et al., Phys. Rev. A 103, 012808 (2021)]. In the present study, we report on the ICEC cross sections at shorter distances which are relevant in biological and biochemical contexts. Furthermore, we investigate the partial ICEC cross sections and demonstrate that the ionization of a water molecule via ICEC is substantially different from that due to direct photoionization. Finally, we show that the distortion of the equilibrium geometry of the water molecule due to the presence of the proton influences the ICEC process.