Electron Photodetachment Research Articles

Observation of bound valence excited electronic states of deprotonated 2-hydroxytriphenylene using photoelectron, photodetachment, and resonant two-photon detachment spectroscopy of cryogenically cooled anions.

Polycyclic aromatic hydrocarbons (PAHs) are common atmospheric pollutants, and they are also ubiquitous in the interstellar medium. Here, we report the study of a complex O-containing PAH anion, the deprotonated 2-hydroxytriphenylene (2-OtPh-), using high-resolution photoelectron imaging and photodetachment spectroscopy of cryogenically cooled anions. Vibrationally resolved photoelectron spectra yield the electron affinity of the 2-OtPh radical as 2.629(1) eV and several vibrational frequencies for its ground electronic state. Photodetachment spectroscopy reveals bound valence excited electronic states for the 2-OtPh- anion, with unprecedentedly rich vibronic features. Evidence is presented for a low-lying triplet state (T1) and two singlet states (S1 and S2) below the detachment threshold. Single-color resonant two-photon photoelectron spectroscopy uncovers rich photophysics for the 2-OtPh- anion, including vibrational relaxation in S1, internal conversion to the ground state of 2-OtPh-, intersystem crossing from S2 to T1, and a long-lived autodetaching shape resonance about 1.3eV above the detachment threshold. The rich electronic structure and photophysics afforded by the current study suggest that 2-OtPh- would be an interesting system for pump-probe experiments to unravel the dynamics of the excited states of this complex PAH anion.

Inglet oxygen generaion via silver nanoparticles UV-photoexcitation

The NIR-luminescence of suspension of silver nanoparticles stabilized in distilled water has been investigated by photoexcitation of surface plasmon resonance (SPR). The observed short-living luminescence with the spectral maximum at 1300 nm is attributed to the singlet oxugen molecules luminescence. The singlet oxygen generation is assumed to pass in two stages as a result of three-photon process. First the one-photon SPR excitation of silver nanoparticle is occurred and leads to superoxide oxygen generation on the nanoparticle surface. Next the superoxide anion absorbs two more photons of the same laser pulse resulting in electron photodetachment with singlet oxygen formation. During a long period of UV-irradiation the studying suspension ceases to be photostable and sedimentation occurs. The sedimentation may be related to disturbance of nanoparticles steric stability resulting in more efficient superoxide anion adsorption on nanoparticles surface with silver oxide formation.

A High-Throughput Workflow for Mass Spectrometry Analysis of Nucleic Acids by Nanoflow Desalting.

Broad interest in nucleic acids, both their therapeutic capabilities and understanding the nuances of their structure and resulting function, has increased in recent years. Post-transcriptional modifications, in particular, have become an important analysis target, as these covalent modifications to the sugars, nitrogenous bases, and phosphate backbone impart differential functionality to synthetic and biological nucleic acids. Characterizing these post-transcriptional modifications can be difficult with traditional sequencing workflows; however, advancements in top-down mass spectrometry address these challenges. Online desalting platforms have enabled facile sample cleanup and reliable ionization of increasingly large (100 nt) oligonucleotides, and application of existing tandem mass spectrometry techniques has yielded information-rich spectra which can be used to interrogate primary sequences. To extend the capabilities of top-down MS and its analysis of nucleic acids, we have developed a nanoflow desalting platform for high-throughput and low sample-use desalting coupled with collision-induced dissociation (CID), 213 nm ultraviolet photodissociation (UVPD), and activated-ion electron photodetachment dissociation (a-EPD) to yield high-quality MS/MS spectra. Fragments identified using an m/z-domain isotope matching strategy yielded high sequence coverage (>70%) of a yeast phenylalanine tRNA.

Study and development of diagnostic systems to characterise the extraction region in SPIDER

SPIDER, an RF-driven negative ion source in the Neutral Beam Test Facility (NBTF), serves as the prototype for ITER's neutral beam injector (NBI). It is composed of 8 drivers powered by 4 RF generators, aiming to accelerate 50 A of negative hydrogen ions to 100 KeV with a beam uniformity target of 10%. The experiment, launched in 2018, tested negative ion production using caesium. Results match those of similar facilities, but SPIDER faces challenges due to its size, multiple drivers, and non-uniform plasma expansion. These issues impact beam uniformity, preventing the machine from reaching expected performance. To address this, SPIDER initiated a significant shutdown at the end of 2021 for improvements.One the most important aspects studied during the first experimental campaign is source uniformity, addressed both in terms of plasma and of caesium distribution. The latter is particularly relevant since its quality is directly related to the beam uniformity and divergence. To have more insight about these issues, monitoring the plasma properties in the extraction region is crucial, hence in the present contribution, the design and development of two new diagnostic systems are described: a movable Langmuir probe and a Retarding Field Energy Analyser (RFEA).The first can provide a vertical scan of the main plasma parameters close to the plasma grid. The spatial resolution would improve with respect to the already installed set of fixed Langmuir probes embedded in the grid system, and the newly installed diagnostic could interact with other sensors to produce complementary measurements (namely, electron photo-detachment).The latter, instead, allows the monitoring of the positive ion energy distribution: positive ions, in fact, can be precursors of the negative ones produced at the caesiated surface, but also influence the energy of negative ion and their extraction probability and thus collecting information about their energy distribution allows inferring details about the extracted negative ion beam.The two diagnostics are designed focusing on the experimental constraint of integrating the diagnostics in a harsh and complex environment such as SPIDER plasma: a preliminary study of the placement inside the source is carried out, then the electrode of the movable probe and the RFEA sensor are sized according to the spatial and energy resolution requested by the system.

Schottky effect on the wavelength threshold for the photo-detachment from charged metallic nanoparticles

Laser-stimulated electron photo-detachment (LSPD) from nanoscale dust particles is predicted to strongly depend on the particle size. A theory of the electron photo-detachment from charged spherical metallic nanoparticles is presented. This theory is relevant to laser-stimulated photo-detachment applied to measurements of charge of nanoparticles in plasmas. Our theory predicts that the charging of nanoparticles in plasma leads to the appearance of an additional electric field, causing a change in the potential barrier at the particle boundary and consequently, a change in the effective work function, due to the Schottky effect. In this case, the critical wavelength of the laser depends not only on the work function, but also on the charge of the nanoparticles and their size.

Top-Down Mass Spectrometry of Synthetic Single Guide Ribonucleic Acids Enabled by Facile Sample Clean-Up.

In recent years, CRISPR-Cas9 genome editing has become an important technology in biomedical research and has demonstrated tremendous therapeutic potential. With Cas9 endonuclease, the use of single guide ribonucleic acids (sgRNAs) allows for sequence-specific cutting on target double-stranded deoxyribonucleic acids. Therefore, the design and quality of sgRNAs can greatly affect the efficiency and specificity of genome editing. Mass spectrometry (MS) has been a powerful tool to detect molecular features and sequence a variety of biomolecules; however, as the sizes of oligonucleotides get larger, it becomes more challenging to desalt samples and achieve high-quality intact spectra with effective fragmentation. Here, we develop a simple but effective online column-based clean-up method (reversed-phase column in a size exclusion mode) that removes formulation salts and metal adducts from larger oligonucleotides upon entering the mass spectrometer in a consistent manner. Using the top-down approach without any nuclease digestion, we characterized and sequenced 100-nucleotide-long sgRNAs by higher-energy collision dissociation (HCD), collision-induced dissociation (CID), ultraviolet photodissociation (UVPD), and activated electron photodetachment (a-EPD). In a single 10 min liquid chromatography-tandem MS (LC-MS/MS) run, CID yielded the best sequence coverage, of 67%. When adding complementary UVPD and a-EPD runs, we achieved 80% overall sequence coverage and 100% cleavages for the variable sequence, the first 20 nucleotides from the 5' end. This LC-MS/MS platform provides a facile top-down workflow to analyze and sequence larger chemically modified oligonucleotides with no sample treatment.

Theoretical and Experimental Study of the Spectroscopy and Thermochemistry of UC+/0/.

A combination of high-level ab initio calculations and anion photoelectron detachment (PD) measurements is reported for the UC, UC-, and UC+ molecules. To better compare the theoretical values with the experimental photoelectron spectrum (PES), a value of 1.493 eV for the adiabatic electron affinity (AEA) of UC was calculated at the Feller-Peterson-Dixon (FPD) level. The lowest vertical detachment energy (VDE) is predicted to be 1.500 eV compared to the experimental value of 1.487 ± 0.035 eV. A shoulder to lower energy in the experimental PD spectrum with the 355 nm laser can be assigned to a combination of low-lying excited states of UC- and excited vibrational states. The VDEs calculated for the low-lying excited electronic states of UC at the SO-CASPT2 level are consistent with the observed additional electron binding energies at 1.990, 2.112, 2.316, and 3.760 eV. Potential energy curves for the Ω states and the associated spectroscopic properties are also reported. Compared to UN and UN+, the bond dissociation energy (BDE) of UC (411.3 kJ/mol) is predicted to be considerably lower. The natural bond orbitals (NBO) calculations show that the UC0/+/- molecules have a bond order of 2.5 with their ground-state configuration arising from changes in the oxidation state of the U atom in terms of the 7s orbital occupation: UC (5f27s1), UC- (5f27s2), and UC+ (5f27s0). The behavior of the UN and UC sequence of molecules and anions differs from the corresponding sequences for UO and UF.

Photodetachment of the outer-most electron(s) in few-electron atomic systems. Variational principle for the cross sections

Photodetachment of the outer-most electron(s) in few-electron atomic systems. Variational principle for the cross sections

On Photoeffect in the Few-Electron Atomic Systems

Closed analytical formulas are derived for the differential and total cross sections of the non-relativistic photoelectric effect in the three main classes of few-electron atomic systems: (a) neutral atoms and positively charged atomic ions which contain more than one bound electron, (b) negatively charged atomic ions, and (c) one-electron atoms and ions. Our procedure developed in this study is a combination of QED methods and results of the density functional theory obtained for atoms and ions. In all these systems the photoelectric effect is considered as photodetachment of the outer-most electron and our analysis is based on the results of density functional theory obtained for the electron density (radial) distribution in these atomic systems. Analytical formulas (similar to ours) for the differential and total cross sections of photoelectric effect for atomic systems from classes (a) and (b) contribute to our understanding of these systems and have not appeared in the literature, to the best of our knowledge.

A 45-degree ion-extraction photoelectron velocity map imaging apparatus coupled to the DUV-IR mass spectrometry and spectroscopy instrument

A photoelectron velocity-map imaging (VMI) apparatus has been developed from the DUV-IR photoionization mass spectrometry and spectroscopy instrument. A 45-degree plate-set is designed and combined with the upright reflection time-of-flight mass spectrometer (Re-TOFMS) to pick up target cluster anions and change their trajectory after the vertical reflection. Following the ion-extraction zone, the mass-selected cluster anions then pass through up-down and left-right trajectory adjustment and beam focus until the arrival at the photoelectron detachment zone to encounter the normal incidence of a pulsed UV laser. The detached electrons are subject to acceleration and detected by a dual micro-channel plate detector and imaging on the phosphor screen. This 45-degree ion-extraction photoelectron VMI setup not only expands the function of our DUV-IR instrument for structural chemistry but also facilitates the compatibility with the conventional upright reflection of TOFMS.

Resonances in nitrobenzene probed by the electron attachment to neutral and by the photodetachment from anion.

We probe resonances (transient anions) in nitrobenzene with the focus on the electron emission from these. Experimentally, we populate resonances in two ways: either by the impact of free electrons on the neutral molecule or by the photoexcitation of the bound molecular anion. These two excitation means lead to transient anions in different initial geometries. In both cases, the anions decay by electron emission and we record the electron spectra. Several types of emission are recognized, differing by the way in which the resulting molecule is vibrationally excited. In the excitation of specific vibrational modes, distinctly different modes are visible in electron collision and photodetachment experiments. The unspecific vibrational excitation, which leads to the emission of thermal electrons following the internal vibrational redistribution, shows similar features in both experiments. A model for the thermal emission based on a detailed balance principle agrees with the experimental findings very well. Finally, a similar behavior in the two experiments is also observed for a third type of electron emission, the vibrational autodetachment, which yields electrons with constant final energies over a broad range of excitation energies. The entrance channels for the vibrational autodetachment are examined in detail, and they point to a new mechanism involving a reverse valence to non-valence internal conversion.

Electron Binding Energy Spectra of AlnPt- Clusters─A Combined Experimental and Computational Study.

Results of size-selected electron photo-detachment experiments and density functional theory calculations on anionic AlnPt-, n = 1-7, clusters are presented and analyzed. The measured and calculated spectra of electron binding energies are, overall, in excellent accord with each other. The analysis reveals the general importance of accounting for the multiplicity of structural forms of a given-size cluster that can contribute to its measured spectrum, especially when the clusters are fluxional and/or the conditions of the experiment allow for structural transitions. We show that for the systems studied here, the size-specific peculiarities of the measured spectra can be understood in terms of the combined contributions of corresponding different accessible stable equilibrium conformations, bona-fide transition-state configurations, and electronic-crossing structures that may play the role of effective barriers in electronically nonadiabatic dynamics.

Molecular Properties of Thorium Hydrides: Electron Affinities and Thermochemistry.

High-level electronic structure calculations of the ground and low-lying energy electronic states for ThHx and ThHx- for x = 2-5 are reported and compared to available anion photoelectron detachment experiments. The adiabatic electron affinities (EAs) are predicted to be 0.82, 0.88, 0.51, and 2.36 eV for x = 2 to 5, respectively, at the Feller-Peterson-Dixon (FPD) level. The vertical detachment energies (VDEs) are predicted to be 0.84, 0.88, 0.81, and 4.38 eV for x = 2-5, respectively. The corresponding experimental VDEs are 0.871 eV for x = 2, 0.88 eV for x = 3, and 4.09 eV for x = 5. As for ThH, there is a significant spin-orbit (SO) correction for the EA of ThH2, and this correction decreases substantially for x > 2. The observed ThH2- photoelectron spectrum has many transitions as predicted at the CASPT2-SO level. The FPD bond dissociation energies (BDEs) increase from 67 to 75 kcal/mol for x = 2 to x = 4 at the FPD level. The BDE for ThH5 is much lower as it is a complex of H2 with ThH3. The hydride affinities for x = 2 to 4 are all comparable and near 70 kcal/mol. A natural bond orbital analysis is consistent with a significant Th+-H- ionic contribution to the Th-H bonds. There is very little participation of the 5f orbitals in the bonding and the valence electrons on the Th are dominated by 7s and 6d for the neutrals and anions except for ThH2- where there is a significant contribution from the 7p.

Ultraviolet Photodissociation and Activated Electron Photodetachment Mass Spectrometry for Top-Down Sequencing of Modified Oligoribonucleotides.

With the increased development of new RNA-based therapeutics, the need for robust analytical methods for confirming sequences and mapping modifications has accelerated. Characterizing modified ribonucleic acids using mass spectrometry is challenging because diagnostic fragmentation may be suppressed for modified nucleotides, thus hampering complete sequence coverage and the confident localization of modifications. Ultraviolet photodissociation (UVPD) has shown great potential for the characterization of nucleic acids due to extensive backbone fragmentation. Activated electron photodetachment dissociation (a-EPD) has also been used as an alternative to capitalize on the dominant charge-reduction pathway prevalent in UVPD, facilitate dissociation, and produce high abundances of fragment ions. Here, we compare higher-energy collisional activation (HCD), UVPD using 193 and 213 nm photons, and a-EPD for the top-down sequencing of modified nucleic acids, including methylated, phosphorothioate, and locked nucleic acid-modified DNA. The presence of these modifications alters the fragmentation pathways observed upon UVPD and a-EPD, and extensive backbone cleavage is observed that results in the production of fragment ions that retain the modifications and allow them to be pinpointed. LNA and 2'-O-methoxy phosphorothioate modifications caused a significant suppression of fragmentation for UVPD but not for a-EPD, whereas phosphorothioate bonds did not cause any significant suppression for either method. The incorporation of 2'-O-methyl modifications suppressed fragmentation of the antisense strand of patisiran, which resulted in some gaps in sequence coverage. However, UVPD provided the highest sequence coverage when compared to a-EPD.

Actinic Wavelength Action Spectroscopy of the IO- Reaction Intermediate.

Iodinate anions are important in the chemistry of the atmosphere where they are implicated in ozone depletion and particle formation. The atmospheric chemistry of iodine is a complex overlay of neutral-neutral, ion-neutral, and photochemical processes, where many of the reactions and intermediates remain poorly characterized. This study targets the visible spectroscopy and photostability of the gas-phase hypoiodite anion (IO-), the initial product of the I- + O3 reaction, by mass spectrometry equipped with resonance-enhanced photodissociation and total ion-loss action spectroscopies. It is shown that IO- undergoes photodissociation to I- + O (3P) over 637-459 nm (15700-21800 cm-1) because of excitation to the bound first singlet excited state. Electron photodetachment competes with photodissociation above the electron detachment threshold of IO- at 521 nm (19200 cm-1) with peaks corresponding to resonant autodetachment involving the singlet excited state and the ground state of neutral IO possibly mediated by a dipole-bound state.

Mass spectrometry studies of nitrene anions.

Nitrene anions are a class of reactive intermediates that provide a means for studying the corresponding neutral molecules via electron photodetachment spectroscopy and photoelectron spectroscopy. The added electron makes it possible for protected nitrene anions to be manipulated by external electric and magnetic fields of a mass spectrometer. Nitrene anions also display their own unique reactivities as reagents, which have been investigated using ion/molecule reactions. Mass spectrometry of negative ions has thereby provided information on the electronic states, reactivities, and thermochemical properties of nitrene intermediates. This review also includes a discussion of condensed-phase nitrene anions.

Prebiotic photoredox synthesis from carbon dioxide and sulfite.

Carbon dioxide (CO2) is the major carbonaceous component of many planetary atmospheres, including the Earth throughout its history. Carbon fixation chemistry— that reduces CO2 to organics—utilizing hydrogen as stoichiometric reductant usually requires high pressures and temperatures, and yields of products of potential use to nascent biology are low. Here we demonstrate efficient ultraviolet photoredox chemistry between CO2 and sulfite that generates organics and sulfate. The chemistry is initiated by electron photodetachment from sulfite giving sulfite radicals and hydrated electrons, which reduce CO2 to its radical anion. A network of reactions—generating citrate, malate, succinate and tartrate by irradiation of glycolate in the presence of sulfite—was revealed. The simplicity of this carboxysulfitic chemistry and the widespread occurrence and abundance of its feedstocks suggest that it could have readily taken place on the surfaces of rocky planets. The availability of the carboxylate products on early Earth could have driven the development of central carbon metabolism before the advent of biological CO2 fixation.

Self-assembling of the neutral intermediate with chemically bound argon in photoexcited van der Waals complex Ar-I2.

Photodissociation of the van der Waals complex Ar-I2 after excitation into the Rydberg states of I2 has been investigated with velocity map imaging of photofragments. Formation of the translationally hot ions of argon Ar+ with three modes in kinetic energy distribution has been revealed. The measured dependence of the kinetic energy of Ar+ on the pumping photon energy indicates the appearance of Ar+ from three channels of the photodissociation of the linear intermediate Ar+-I-I- containing chemically bound argon. These channels are (1) dissociation into Ar++ I2 -; (2) three-body dissociation into (Ar+)* + I* + I-, with (Ar+)* and I* being the 2P1/2 states of the species; and (3) two-body electron photodetachment, giving rise to Ar+ + I2 + e. Three indicated channels are similar to those established for the photodissociation of trihalide anions. This similarity confirms the conclusion on the formation of the Ar+-I-I- intermediate, which is isoelectronic to the trihalide anion Cl-I-I-. The mechanism of the Ar+-I-I- formation involves two-photon excitation of the complex Ar-I2 into the Rydberg state of I2 converted into the ion-pair state and further electron transfer from Ar to I+ of the ion-pair state. The self-assembling of the structure making the formation of the Ar+-I-I- intermediate energetically accessible is confirmed by modeling the dynamics in the excited linear complex Ar-I2. Photoexcitation of the van der Waals complexes of noble gases with halogens into the ion-pair states of halogen is supposed to be a promising approach for generating the new chemical compounds of noble gas atoms.

Gas-phase heme structure of the singly charged cytochrome c anion produced by IR-laser ablation of a droplet beam

Photoelectron detachment yield (PDY) spectroscopy is an effective tool for elucidating gas phase protein structures compared with other spectroscopies in aqueous solutions. In general, investigations of low-charged ions are necessary to elucidate the intrinsic properties of protein because excess charge perturbs the electronic state of the protein. In this study, we measured PDY spectrum of the most low-charged cytochrome c (cyt c) anion, [cyt c]- by IR-laser ablation of a droplet beam. This result shows a spectral blueshift from the absorption peak of aqueous cyt c and the PDY peak of the [cyt c]6- ion reported in the previous study.

Loss of CO2 from Monodeprotonated Phthalic Acid upon Photodissociation and Dissociative Electron Detachment.

The decarboxylation (CO2 loss) mechanism of cold monodeprotonated phthalic acid was studied in a photodissociation action spectrometer by quantifying mass-selected product anions and neutral particles as a function of the excitation energy. The analysis proceeded by interpreting the translational energy distribution of the generated uncharged products, and with the help of quantum calculations. In particular, this study reveals different fragmentation pathways in the deprotonated anion and in the radical generated upon electron photodetachment. Unlike the behavior found in other deprotonated aryl carboxylic acids, which do not fragment in the anion excited state, a double loss of CO2 molecules takes place in the phthalic monoanion. Moreover, at higher excitation energies the phthalic monoanion experiences decarboxylative photodetachment with a statistical distribution of product translational energies, which contrasts with the impulsive dissociation reactions characteristic of other aryl carboxylic anions.