Ionization Spectroscopy Research Articles

Determination of nuclear charge radius by extreme-ultraviolet spectroscopy of Na-like ions

We report on a method for determining the absolute nuclear charge radius of high-Z elements using extreme-ultraviolet spectroscopy of highly charged Na-like ions in tandem with highly accurate atomic structure calculations of transition energy differences. The application of this method has reduced the nuclear charge radius uncertainty of Ir191 by a factor of 8 from the currently accepted literature value, with a recently reported charge radius of 5.442(12) fm. The result reduces the charge radius uncertainty along the full Ir isotopic chain when combined with prior optical isotope shift measurements. The technique utilizes only a few million ions stored in an ion trap, which should apply to measurements with small quantities of radioactive nuclei. Published by the American Physical Society 2025

Ion momentum mapping in photodissociation and Coulomb explosion events using ion time-of-flight analyzers

Abstract Modern light sources such as free electron lasers allow for tracking photoinduced events with an unprecedented accuracy. Ion spectroscopy is a particularly useful tool, revealing, e.g., momentum correlations in dissociation and Coulomb explosion patterns. Determining ion momentae and their relationship with the highest achievable accuracy is therefore very valuable. Here, we develop a systematic approach of accurate ion momentum determination in Wiley-McLaren type ion time-of-flight spectrometers taking into account also field penetration effects. The developed analytical formulae at various level of approximation are compared with ray tracing simulations and the effects are also illustrated on an experimental example.

A Unique Intramolecular Redox Reaction by Unidirectional Migration of Three Hydrogen Atoms: Theoretical Elucidation of the 3H-Transfer Sequence.

The intramolecular migration of three hydrogen atoms from one moiety of a gaseous radical cation to the other prior to fragmentation is an extremely rare type of redox reaction. Within the scope of this investigation, this scenario requires an ionized but electron-rich arene acceptor bearing a para-(3-hydroxyalkyl) residue. The precise mechanism of such unidirectional 3H transfer processes, including the order of the individual H transfer steps, has remained unclear in spite of previous isotope labelling and recent infrared ion spectroscopy (IRIS) studies. Herein, the details of this peculiar process have been investigated for ionized 4-(N,N-dimethylaminophenyl)-2-butanol, 2, by state-of-the-art density functional theory (DFT) calculations. The energetically most favorable pathway consists of a sequence of successive 1,4-, 1,6- and 1,5-H steps. During these steps the secondary alcohol functionality is oxidized to a carbonyl group and the radical-cationic aniline ring is reduced to an ionized 2,3-dihydroaniline unit. Several alternative sequences, such as three successive 1,5-H shifts, could be excluded. A concomitant unidirectional 2H migration reaction of the ion 2 was also investigated and the intermediacy of ion-neutral complexes (INCs) enabling sequential hydride and proton transfer was confirmed by the calculations.

Atmospheric Pressure Laser Ionization Mass Spectrometry with Tunable UV Wavelength Utilizing an Optical Parametric Oscillator.

To our knowledge, this study presents the first implementation of wavelength-resolved resonance-enhanced multiphoton ionization (REMPI) spectroscopy under atmospheric pressure ionization conditions using a high-resolution mass spectrometric system. Atmospheric pressure laser ionization MS spectroscopic measurements were conducted on over 70 different polycyclic aromatic hydrocarbons (PAHs) and hetero-PAHs (N, S, and O) in standard solutions, as well as three complex PAH-containing samples. The results demonstrate the successful transfer of REMPI spectroscopy from vacuum to atmospheric pressure conditions, maintaining spectral integrity without significant band broadening. The obtained spectral data add an orthogonal dimension to mass spectrometry, providing structural insights into aromatic core motifs and enabling isomeric differentiation. This differentiation is further enhanced by linear regression algorithms, which allow for the semiquantitative analysis of isomer mixtures. Comparison between standard spectra and complex sample spectra reveals high correlation values for certain peaks, strongly indicating the presence of specific PAHs and distinguishing between phenanthrene and anthracene in fossil- and biobased samples.

Triazolide Complexes of Sodium and Potassium in the Gas Phase.

Aromatic organometallic complexes, such as ferrocene and the "inverse sandwich complex" [Na2Cp]+, are stabilized via charge-transfer (C-T) interactions and cation-π interactions (i.e., charge-induced dipole and charge-quadrupole interactions). Much effort has gone into investigating systems that contain organic moieties, such as benzene or cyclopentadienyl ligands, but less attention has been paid to aromatic systems that contain heteroatoms (e.g., N), possibly owing to the complexity arising from a lowering of symmetry and the introduction of electron lone pair density and dipole moments. Here we investigate sodiated and potassiated clusters of 1,2,3-triazolide, [Mx (123T)x-1]+ (x = 3, 4; M = Na, K), and 1,2,4-triazolide, [Mx (124T)x-1]+ (x = 3, 4; M = Na, K), using a combination of infrared ion spectroscopy (IRIS) and DFT calculations. Cluster structures are strongly influenced by charge-dipole interactions and C-T interactions from N lone pairs to the metal cations. IRIS spectra indicated that the geometries of the triazolide moieties are essentially unperturbed by the interaction with the metal ions. Additional spectral features, not predicted by DFT calculations, that are observed in the 1500-1800 cm-1 region seem to be associated with combination bands involving C-H wagging and ring torsion motions.

Spectroscopy and Excited-State Dynamics of Methyl Ferulate in Molecular Beams.

The spectroscopic and dynamic properties of methyl ferulate─a naturally occurring ultraviolet-protecting filter─and microsolvated methyl ferulate have been studied under molecular beam conditions using resonance-enhanced multiphoton ionization spectroscopy in combination with quantum chemical calculations. We demonstrate and rationalize how the phenyl substitution pattern affects the state ordering of the lower excited singlet state manifold and what the underlying reason is for the conformation-dependent Franck-Condon (FC) activity in the UV-excitation spectra. Studies on microsolvated methyl ferulate reveal potential coordination sites and the influence of such coordination on the spectroscopic properties. Our quantum chemical studies also enable us to obtain a quantitative understanding of the dominant excited-state decay routes of the photoexcited ππ* state involving a ∼3 ns intersystem crossing pathway to the triplet manifold─which is much slower than found for coumarates─and a relatively fast intersystem crossing back to the ground state (∼30 ns). We show that a common T1/S0 crossing can very well explain the observation that T1 lifetimes are quasi-independent of the phenyl substitution pattern.

Investigation of magnetospheric solitons in the recovery phase of a geomagnetic storm for solar cycle 23 using Cluster II mission

Abstract Solitary structures or solitons, prominent nonlinear phenomena in space plasmas, have been extensively studied, particularly in the magnetospheric regime utilizing data from Cluster II mission. This study examines aperiodic magnetospheric oscillations observed during the recovery phase of a geomagnetic storm (GMS), which is a result of magnetic disturbances triggered by coronal mass ejection (CME) or interplanetary mass ejection (ICME) interacting with Earth’s magnetic field, in solar cycle 23. The analysis utilizes data from the Fluxgate Magnetometer (FGM) and Cluster Ion Spectroscopy (CIS) instruments onboard spacecraft C1 and C4 of the Cluster II mission. The analysis identifies a train of aperiodic solitons with increasing amplitudes propagating through the bow shock region of the magnetosphere. This paper provides detailed observations and analytical insights into the formation mechanisms of these aperiodic solitons during geomagnetic storm recovery.

Development of a Platform for High-Resolution Ion Mobility Separations Coupled with Messenger Tagging Infrared Spectroscopy for High-Precision Structural Characterizations.

The ability to uniquely identify a compound requires highly precise and orthogonal measurements. Here we describe a newly developed analytical platform that integrates high resolution ion mobility and cryogenic vibrational ion spectroscopy for high-precision structural characterizations. This platform allows for the temporal separation of isomeric/isobaric ions and provides a highly sensitive description of the ion's adopted geometry in the gas phase. The combination of these orthogonal structural measurements yields precise descriptors that can be used to resolve between and confidently identify highly similar ions. The unique benefits of our instrument, which integrates a structures for lossless ion manipulations ion mobility (SLIM IM) device with messenger tagging infrared spectroscopy, include the ability to perform high-resolution ion mobility separations and to record the IR spectra of all ions simultaneously. The SLIM IM device, with its 13 m separation path length, allows for multipass experiments to be performed for increased resolution as needed. It is integrated with an Agilent qTOF MS where the collision cell was replaced with a cryogenically held (30 K) TW-SLIM module. The cryo-SLIM is operated in a novel manner that allows ions to be streamed through the device and collisionally cooled to a temperature where they can form noncovalently bound N2 complexes that are maintained as they exit the device and are detected by the TOF mass analyzer. The instrument can be operated in two modes: IMS+IR where the IR spectra for mobility-selected ions can be recorded and IR-only mode where the IR spectra for all mass-resolved ions can be recorded. In IR-only mode, IR spectra (400 cm-1 spectral range) can be recorded in as short as 2 s for high throughput measurements. This work details the construction of the instrument and modes of operation. It provides initial benchmarking of CCS and IR measurements to demonstrate the utility of this instrument for targeted and untargeted approaches.

Intramolecular Polarization Contributions to the pKa's of Carboxylic Acids Through the Chain Length Dependence of Vibrational Tag-Shifts in Cryogenically Cooled Pyridinium-(CH2)n-COOH (n = 1-7) Cations.

The pKa's of acids are known to depend on the ionic strength of an electrolyte solution, an effect that qualitatively results from electrostatic interactions of the acid and conjugate base with proximal ions. Here, we explore an intramolecular variation on this theme in which a carboxylic acid group is tethered to a pyridinium cationic charge center with increasingly long alkyl linkages in the series Py+-(CH2)n-COOH, with n = 1-7. The effective acidities of the carboxylic acid group in the isolated cations are determined by recording the red-shifts in the frequencies of the acid OH stretches upon attachment to D2 and N2 molecules, measured by using cryogenic ion spectroscopy. The short chains indeed lead to substantial increases in acidity, with the effect falling off in the range of n = 4-5. The response of the CO stretch on the acid head group is surprisingly strong and, in contrast to the expected red shift of the OH, displays a blue shift as the chain length is reduced. Electronic structure calculations recover these trends and indicate that the proximal cationic charge center acts to draw electron density away from the acid C═O bond. This acts to blue-shift the CO stretch while weakening the C-C bond that attaches the head group to the chain.

Impact of chlorine substitution on valence orbitals and ionization dynamics in 3-chloropyridine: Insights from high-resolution vacuum ultraviolet mass-analyzed threshold ionization study.

In this study, the effects of chlorine substitution on the valence orbitals and electronic states of 3-chloropyridine (3-CP) were investigated utilizing high-resolution vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy and computational methods. High-quality vibrational spectra were obtained from the VUV-MATI spectra of 3-CP isotopomers (35Cl and 37Cl), revealing high-quality vibrational spectra for the lowest cationic states. The adiabatic ionization energies (AIEs) of these isotopomers were accurately determined, providing detailed information about the electronic structure and ionization dynamics. Intense spectra peaks were linked with the D1 excited state of the 3-CP cation, with vibronic transitions in this state closely matching those predicted by Franck-Condon simulations. This provided insights into the cationic structure and the roles of the highest occupied molecular orbital (HOMO) and the HOMO-1. The HOMO was primarily a π orbital of the pyridine ring, while the HOMO-1 consisted of nonbonding orbitals. The AIEs suggested that meta-chlorine substitution stabilizes nonbonding orbitals less effectively than ortho substitution, indicating closely spaced electronic states in the 3-CP cation. Minor discrepancies in vibrational frequencies and intensities, particularly above 800cm-1, suggested the presence of vibronic coupling, warranting further investigation. Overall, this study provided a comprehensive understanding of the vibronic and ionization properties of 3-CP, emphasizing the influence of the position of the chlorine substitution on molecular orbitals and the value of advanced theoretical and experimental approaches for analyzing the vibrational spectra of complex molecules.

Vibrational assignments and energy analyses of 3,4-difluorophenylacetylene using resonance-enhanced multiphoton ionization and slow electron velocity-map imaging techniques

Here, we report spectroscopic investigations of 3,4-difluorophenylacetylene applying two-color resonant two-photon ionization (2C-R2PI) and slow electron velocity-map imaging (SEVI) techniques. With the assistance of density functional theory (DFT) calculations, vibrational modes of the S0 neutral ground state, S1 first electronic excited state, and D0 cationic ground state were assigned. The adiabatic excitation energy of the S1 ← S0 electronic transition was determined to be 35639 ± 5 cm−1 from the resonance-enhanced multiphoton ionization (REMPI) spectroscopy. Additionally, the adiabatic ionization potential was found to be 72398 ± 5 cm−1 based on the SEVI spectra.

Investigation of Neighboring Group Participation in 3,4-Diacetylated Glycosyl Donors in the Gas Phase.

A key challenge in oligosaccharide synthesis is the stereoselective installation of glycosidic bonds. Each glycosidic linkage has one of two possible stereo-chemical geometries, α/β or 1,2-cis/trans. An established approach to install 1,2-trans glycosidic bonds is neighboring group participation (NGP), mediated by a 2-O-acyl group. Extension of this intramolecular stabilization to nucleophilic groups located at more remote positions has also been suggested, but remains poorly understood. Previously, we employed infrared ion spectroscopy to characterize the molecular ions of monoacetylated sugar donors and showed how the strength of the stabilizing effect depends on the position of the participating ester group on the glycosyl donor ring as well as on its relative stereochemistry. In this work, we investigated glycosyl donors carrying two acyl groups. Using isotope labelling and isomer population analysis we were able to resolving spectra of isomeric mixtures and establish the relative contribution of individual species. We conclude that 3,4-diacetyl mannosyl donors exclusively form a dioxanium ion as a result of C-3 acyl stabilization. In contrast, the glucosyl and galactosyl cations form mixtures of C-3 and C-4 acyl participation products. Hence, the combination of isotope labeling and population analysis allows for the study of increasingly complex glycosyl cations.

Laser Spectroscopic Characterization of Supersonic Jet-Cooled 2,6-Diazaindole (26DAI).

The article presents a comprehensive laser spectroscopic characterization of a nitrogen-rich indole derivative, namely, 2,6-diazaindole (26DAI), in the gas phase. A supersonic jet-cooled molecular beam of 26DAI was characterized using two-color resonant two-photon ionization (2C-R2PI) and laser-induced fluorescence spectroscopy (LIF) to investigate the electronic excitation. The S1 ← S0 origin transition was obtained at 33915 cm-1, which was red-shifted from that of one (indole) and two (7-azaindole) nitrogen-containing indole derivatives by 1317 and 713 cm-1, respectively. The molecular orbital and energy analysis for the S1 ← S0 transition shows the significant stabilization of LUMO on subsequent N-insertion, resulting in the lowering of the S1 ← S0 (ππ*) transition energy. The single vibronic level fluorescence spectrum from the vibrationless S1 state of the molecule was recorded. The spectrum displayed an extensive Franck-Condon activity until 2500 cm-1 for the vibrational modes of the S0 state of the 26DAI molecule. The experimental ground state vibrational frequencies were compared to the calculated ones obtained at three different levels of theories. More accurate results were found at DFT B3LYP-D4 than those at the wave function-based MP2 and CCSD levels of theories. Further, the N-H stretching frequency of 26DAI in the S0 state was measured at 3524 cm-1 using fluorescence-dip infrared (FDIR) spectroscopy. The stability of 26DAI against ionization radiation was probed by measuring the two-color photoionization energy (IE2P) of 26DAI at 71866 cm-1. The IE2P value is significantly higher than those of N-poor counterparts (indole and 7-azaindole). The NBO charges and spin density (SD) values of the 26DAI molecule have shown that electronegative N(6) makes the cationic ground state less stable due to the position of the positive centers on the N atom. The results provided insights into the stability of N-rich biomolecules against photodamage. The current investigation can shed light on nature's way of stabilizing biomolecules with a possible N-insertion mechanism.

Resonance ionization spectroscopy of neodymium for determining a highly efficient two-step ionization scheme

Two-color two-step resonance ionization spectroscopy of neodymium (Nd) was performed to identify more than 120 even-parity autoionizing levels and their candidate J-values. The analysis of the observed autoionizing Rydberg series yielded a value of 44,560.11 (43)stat (2)sys cm−1 as a more accurate ionization potential of Nd. The saturation method was used to measure the transition cross-sections for some intense ionization transitions. From the measured cross-sections, the ionization efficiencies of some two-step ionization schemes were evaluated using the scheme cross-section formula to obtain several promising schemes.

Isomeric Speciation of Bisbenzoxazine Intermediates by Ion Spectroscopy and Ion Mobility Mass Spectrometry.

Bisbenzoxazines (BisBz) are a relevant model for the diverse bifunctional benzoxazines that are used to increase the polybenzoxazines cross-linking extensions and modulate the final resin properties for various usages. The presence of side products and intermediates during monomer formation can influence the resin characteristics by inducing chain termination and ramifications, affecting the polymerization and cure processes. This work investigated the diverse isomeric intermediates and side products that are present during the BisBz formation from bisphenol A, aniline, and formaldehyde by ion mobility coupled to tandem mass spectrometry (MS/MS) and ion spectroscopy techniques. The species detected in this work suggest that these multifunctional phenols open diverse concurrent reaction pathways based on two main reactive steps: (i) the imine/iminium phenol attack to form a phenylamino intermediate and (ii) the formaldehyde attack followed by dehydration to form the oxazine ring. The species observed also support previous studies of the benzoxazine formation mechanism and showcase the application of advanced analytical techniques in studying complex chemical systems.

Determination of chromium traces by atomic ionization spectroscopy in aqueous standard solutions and in gallium arsenide using the «rod – flame» atomization system

The results of the determination of trace amounts of chromium in aqueous standard solutions of chromium and in high purity gallium arsenide using atomic ionization spectroscopy are presented. Single — and two-step schemes of chromium atom excitation from the ground state 3d54s 7S3 to septet states 3d54p 7P2,3,4, 3d44s4p 7P2,3,4 were studied using a «rod – flame» atomizer. A mechanism of forming atomic-ionization signal for two-step excitation schemes is revealed. The most effective two step excitation schemes for chromium atoms were determined and experimentally studied at different wavelengths λ1 = 425.4 nm, λ2 = 451.4 nm; λ1 = 425.4 nm, λ2 = 426.1 nm. The low limit of chromium detection in aqueous water solutions was 50 pg/ml. The analytical potentiality of the «rod – flame» system for determining traces of chromium in gallium arsenide solutions has been demonstrated. The possibility of determining traces of chromium in gallium arsenide using a flame – rod atomizer at a level of 5 × 10–7 % is demonstrated. Two methods are proposed to increase the selectivity and sensitivity of atomic-ionization determination of chromium: optimization of the temperature program of the flame – rod atomizer and the use of two-stage excitation of chromium atoms. It is shown that the main interfering factor is the background attributed to the matrix ionization. Methods are proposed to reduce or eliminate the matrix impact, which ensure direct determination of elements in samples.

A trapped ion mobility enabled Fourier transform ion cyclotron resonance mass spectrometer for infrared ion spectroscopy at FELIX

We report the installation of a new infrared ion spectroscopy platform at the free-electron laser facility FELIX, based on a Bruker SolariX Fourier Transform ion cyclotron resonance (FT-ICR) mass spectrometer equipped with a trapped ion mobility spectrometry (TIMS) stage. The instrument allows one to record infrared multiple-photon dissociation (IRMPD) spectra for mass and mobility selected ions, produced by a range of ion sources. We describe two strategies to achieve consistent overlap between the laser beam and the ion packet. Removing the original ECD cathode significantly enhanced the IR transmission and the overlap with the ion cloud, resulting in improved IRMPD yield per pulse. Enhancement of the photodissociation yield is observed when multiple pulses are used, as there is negligible collisional deactivation in the ultra-high vacuum trapping region of the ICR cell. We compare IRMPD spectra recorded on the new platform with IRMPD spectra of the same species recorded on one of our 3D-quadrupole ion trap platforms. We demonstrate the instrument’s performance using a sample containing a mixture of two trisaccharides. Mobility selection allows us to record individual IR spectra for the two isomeric species. This multi-modal platform, encompassing liquid chromatography, ion mobility spectrometry, ultra-high resolution (tandem) mass spectrometry, infrared ion spectroscopy (and soon also mass spectrometry imaging), is available to users at the FELIX facility.

(Invited) Stabilizing the Electrodes and Interfaces in Lithium-Sulfur Batteries

As the electrification of transportation sector and grid storage of electricity produced from renewable sources like solar and wind are rapidly evolving, cost, sustainability, and supply chain challenges will become the dominant issue. Lithium-sulfur batteries offer significant sustainability and cost advantages compared to the currently used lithium-ion batteries as sulfur is abundant and inexpensive and offers an order of magnitude higher capacity than the oxide cathodes. However, the commercialization of lithium-sulfur batteries is met with a few challenges, such as poor cycle life in practical cells. These challenges originate from the poor electronic and ionic conduction in sulfur and its discharged products, polysulfide shuttle, and poor cyclability of lithium-metal anode. To overcome some of these difficulties, generally a large amount of conductive carbon and liquid electrolyte are added to the cell; they enhance the cycle life, but drastically lower the practical energy density and make the lithium-sulfur batteries uncompetitive with lithium-ion batteries. To overcome the above challenges, this presentation will focus on optimizing sulfur and lithium sulfide cathodes, incorporation of electrocatalysts into the cathode to enhance sulfur redox, development of advanced electrolytes, incorporation of additives into the cathode and electrolyte to stabilize the cathode-electrolyte and anode-electrolyte interfaces, anode-free cells that eliminate the handling of thin lithium-metal foils, while keeping the sulfur loading and electrolyte/sulfur ratio at a practically accepted level. The improvements achieved and the mechanisms involved in the performance improvement will be discussed based on in-depth characterization data obtained with time-of-flight secondary ion spectrometry (TOF-SIMS), x-ray photoelectron spectroscopy (XPS), nuclear magnetic resonance (NMR) spectroscopy, etc.

Spectroscopic and computational characterization of lanthanide-mediated bond activation of ethylamine

Ln (Ln = La and Ce) atom reactions with ethylamine are conducted in a pulsed laser vaporization supersonic molecular beam source. Dehydrogenation and association metal-containing species are observed with time-of-flight mass spectrometry, and the dehydrogenated Ln ethylimido species in the formula Ln(NC2H5) are characterized by single-photon mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. The theoretical calculations include density functional theory for both Ln species and a scalar relativity correction, electron correlation, and spin-orbit coupling through multiconfiguration quasi-degenerate second-order perturbation theory for the Ce species. The MATI spectrum of lanthanum ethylimido La(NCH2CH3) has a single vibronic band system from the ionization of the doublet ground state with the La 6s1 configuration, whereas that of the cerium ethylimido Ce(NCH2CH3) displays two vibronic band system from the ionization of the two lowest-energy spin-orbit coupling states with the Ce 4f16s1 configuration. Both Ln ethylimido complexes are formed by the thermodynamically and kinetically favorable concerted dehydrogenation of the amino group. Two additional isomers of Ln(NC2H5) include a four-membered metallacycle Ln(NHCH2CH2) from the dehydrogenation of the amino and methyl groups and a three-membered cycle Ln(NHCHCH3) from the dehydrogenation of the amino and methylene groups. The cyclic isomers are not observed experimentally as they are not populated under the experimental conditions.

Micro Solvation Effect of Methanol on Excited-State Dynamics of Protonated Tryptophan and Dopamine.

The electronic and vibrational cryogenic ion spectroscopy of protonated tryptophan (TrpH+) and dopamine (DAH+) complexed with methanol has been recorded. These two biological chromophores exhibit ultrafast photochemistry due to excited-state proton transfer (ESPT). We have established the relationship between the structure of the complexes and their photodynamics and compared them with recent results obtained in hydrated complexes. For TrpH+, there is no substantial change between methanol and water complexes; ESPT is hindered by a single solvent molecule. In the DAH+(MeOH)1 complex, the most stable conformer adopts a structure that prevents the direct interaction of the ammonium group of the side chain with the catechol ring, thus blocking the ESPT reaction. Such a ring structure is indeed a very minor populated conformer in the single-hydrated complex. The change in conformal stability between water and methanol clusters is due to a weak CH-π attractive interaction of the methyl group of methanol with the catechol.