Molecular Ions Research Articles

Sub-attosecond time delays of photoemission from asymmetric cores of molecules

We theoretically study the extreme ultraviolet (XUV) photoemission of the asymmetric molecular ion HeH2+ beyond the dipole approximation. Based on the double-slit interference of the photoelectron emitted from two atomic cores, we propose a scheme to obtain the XUV photoemission time delays originated from different physical mechanisms. In our study, two types of sub-attosecond photoemission time delays are identified and extracted from the observable photoelectron momentum distributions. One is the so-called birth time delay, originated from the travel time of the photon across the molecule, and the other is the escaping time delay of the photoelectron from two different cores. The present study shows the observable evidence demonstrating that in single-photon ionization, it takes more time for the photoelectron escaping from the helium nucleus than that from the proton. Published by the American Physical Society 2024

Production and purification of molecular 225Ac at CERN-ISOLDE

AbstractThe radioactive nuclide 225Ac is one of the few promising candidates for cancer treatment by targeted-$$\alpha$$ α -therapy, but worldwide production of 225Ac faces significant limitations. In this work, the Isotope Separation On-Line method was used to produce actinium by irradiating targets made of uranium carbide and thorium carbide with 1.4-GeV protons. Actinium fluoride molecules were formed, ionized through electron impact, then extracted and mass-separated as a beam of molecular ions. The composition of the mass-selected ion beam was verified using time-of-flight mass spectrometry, $$\alpha$$ α - and $$\gamma$$ γ -ray decay spectrometry. Extracted quantities of $$^{225}\textrm{Ac}^{19}\textrm{F}_2^{+}$$ 225 Ac 19 F 2 + particles per $$\upmu$$ μ C of incident protons were $$3.9(3)\times 10^7$$ 3.9 ( 3 ) × 10 7 from a uranium carbide target and $$4.3(4)\times 10^7$$ 4.3 ( 4 ) × 10 7 for a thorium carbide target. Using a magnetic mass separator, the long-lived contamination 227 Ac is suppressed to $$<5.47\times 10^{-7}$$ < 5.47 × 10 - 7 (95% confidence interval) with respect to 225Ac by activity. Measured rates scale to collections of 108 kBq$$\upmu$$ μ A$$^{-1}$$ - 1 h$$^{-1}$$ - 1 of directly produced $$^{225}\textrm{Ac}^{19}\textrm{F}_2^{+}$$ 225 Ac 19 F 2 + .

Bell Test of Quantum Entanglement in Attosecond Photoionization

Attosecond physics enables the study of ultrafast coherent electron dynamics in matter upon photoexcitation and photoionization, revealing spectacular effects such as hole migration and coherent Auger dynamics in molecules. In the photoionization scenario, there has been a strong focus on probing the physical manifestations of internal quantum coherence within the individual parent ion and photoelectron systems. However, quantum correlations between these two subsystems emerging from attosecond photoionization events have thus far remained much more elusive. In this work, we design theoretically and model numerically a direct probe of quantum entanglement in attosecond photoionization in the form of a Bell test. We simulate from first principles a Bell test protocol for the case of noble gas atoms photoionized by ultrashort, circularly polarized infrared laser pulses in the strong-field regime predicting robust violation of the Bell inequality. This theoretical result paves the way for the direct observation of entanglement in the context of ultrafast photoionization of many-electron systems. Our work provides a novel perspective on attosecond physics directed toward the detection of quantum correlations between systems born during attosecond photoionization and unraveling the signatures of entanglement in ultrafast coherent molecular dynamics, including in the chemical decomposition pathways of molecular ions. Published by the American Physical Society 2024

A Smart Polycage Membrane with Responsive Osmotic Energy Conversion Based on Synchronously Switchable Microporosity and Chargeability.

Membranes with specific pore sizes are widely used in molecular separation, ion transport, and energy conversion. However, the molecular understanding of structure-property performance in membrane science has been an urgent and long-standing problem. A promising but challenging solution lies in the fine-tuning of the membrane microstructure and properties to control membrane performance. Here, we designed an exofunctionalized triskelion cage to construct smart polycage membranes with concurrently responsive pore apertures and charge property. The synthetic polyaza cage is decorated with exoextended aldehyde groups for membrane fabrication and multiple amine sites for postmodification. The engineered polycage membranes thereby are endowed with pH-responsive porosity and chargeability, which serve as excellent candidates to explore the influence of the pore size and charge properties on membrane performance. In this regard, we successfully demonstrated the responsive osmotic energy conversion of the polycage membrane with a power density increase of over fourfold. This result indicates that the chargeability here outcompetes microporosity in energy conversion performance, which is further supported by molecular simulations. Therefore, this smart polycage membrane not only offers a feasible strategy to regulate the membrane microstructure and charge property reversibly but also balances pore size and chargeability to control the membrane performance at the molecular level.

Atom Probe Tomography: a Local Probe for Chemical Bonds in Solids.

Atom probe tomography is frequently employed to characterize the elemental distribution in solids with atomic resolution. Here the potential of this technique to locally probe chemical bonds is reviewed and discussed. Two processes characterize the bond rupture in laser-assisted field emission, the probability of molecular ions (PMI), i.e., the probability that molecular ions are evaporated instead of single (atomic) ions, and the probability of multiple events (PME), i.e., the correlated field-evaporation of more than a single fragment upon laser- or voltage pulse excitation. Here it is demonstrated that one can clearly distinguish solids with metallic, covalent, and metavalent bonds based on their bond rupture, i.e., their PME and PMI values. These findings open new avenues in understanding and designing advanced materials, since they allow a quantification of bonds in solids on a nanometer scale, as will be shown for several examples. These possibilities would even justify calling the present approach bonding probe tomography (BPT).

Effect of hyaluronic acid on the formation of acellular dermal matrix-based interpenetrating network sponge scaffolds for accelerating diabetic wound healing through photothermal warm bath

Adequate vascularization essential for delivering nutrients critical to wound healing, yet impaired angiogenesis is a major barrier in diabetic wound repair. This study investigates the impact of hyaluronic acid on interpenetrating network sponge scaffolds derived from an acellular dermal matrix, with the aim of enhancing vascularization and healing of diabetic wounds via photothermal warm bath therapy. We prepared three-dimensional porous sponges (H1P4D2@DFO) using molecular interpenetration and ion crosslinking of porcine acellular dermal matrix (PADM), hyaluronic acid, and polydopamine nanoparticles loaded with deferoxamine mesylate (PDA@DFO). This resulting extracellular matrix-based sponge demonstrated properties suitable for wound repair, including high cell adhesion, biocompatibility, bioactivity, porosity (85 %), and water absorption (4500 %). The near-infrared (NIR) photothermal effect of PDA@DFO and the sustained release of deferoxamine mesylate (DFO) enhanced wound vascularization within the wound site. These findings suggest that our sponge scaffold can simulate skin-like structures and establish a supportive microenvironment conducive to microvascular reconstruction. By combining the photothermal warm bath approach with the scaffold's tailored 3D structure, we observed enhanced angiogenesis and accelerated diabetic wound healing, indicating potential clinical applications of these scaffolds in chronic wound management.

Back-decay of the muonic molecular ion (αμt)012+ resonantly formed in (tμ)1s+4HeH+ collision

Abstract Resonant formation of the muonic molecular ion ( α μ t ) 01 2 + in the collision of the muonic tritium atom with the helium hydride ion, ( t μ ) 1 s + 4 HeH + → [ ( α μ t ) 01 2 + , p , e e ] + , is proposed. The ( α μ t ) 01 2 + ion is formed in the rotational-vibrational state (0,1) as one of the two nuclei of the final complex. Back-decay process [ ( α μ t ) 01 2 + , p , e e ] K n + → ( t μ ) 1 s + 4 HeH K ′ n ′ + , where K and n ( K ′ and n ′ ) is the rotational and vibrational quantum number, respectively, is considered in detail and the corresponding decay widths for all possible rotational-vibrational ( K , n ) → ( K ′ , n ′ ) transitions are calculated. Numerous inelastic decay channels of ( α μ t ) 01 2 + are also presented and discussed. The possible fast resonant formation of the ( α μ t ) 01 2 + ion may provide an interesting tool for experimental studies of t ( α , γ ) 7 Li nuclear fusion, which is one of the most important reactions in Big-Bang nucleosynthesis models. Studying this reaction may prove important for solving the lithium problem.

Measurements of F1‐ Region Ionosphere State Variables at Arecibo Through Quasi Height‐Independent Exhaustive Fittings of the Incoherent Scatter Ion‐Line Spectra

AbstractWe discuss an exhaustive search approach to fit the incoherent scatter spectrum (ISS) in the F1‐region for molecular ion fraction (fm), ion temperature (Ti), and electron temperature (Te). The commonly used “full profile” approach for F1‐region measurements parameterizes the molecular ion fraction as a function of altitude and fits all the related heights for the state variables. In our approach, we fit the ISS at each height for fm, Ti, Te, and ion velocity (Vi) independently. Our exhaustive search method finds all the major local minima at each altitude. Although a parameterized function is used to guide the algorithm in finding the best solution, the fitting parameters retain their local characteristics. Despite that fitting fm, Ti, and Te without constraints requires Doppler shift to be accurately determined and the ISS signal‐to‐noise ratio higher than the full‐profile method, simulations show that Ti, Te, and fm can be recovered within a few percent accuracy with a moderate signal‐to‐noise ratio. We apply the exhaustive search approach to the Arecibo high‐resolution incoherent scatter radar data taken on 13 September 2014. The derived ion and electron temperatures are sensitive enough to reveal thermosphere gravity waves commonly seen in the electron density previously. Our method is more robust than previous height‐independent fitting methods. Comparison with another Arecibo program indicates our results are likely more accurate. Simultaneous high‐resolution measurements of Ti, Te, fm, Vi, and electron concentration (Ne) in our approach open new opportunities for synergistic studies of the F1‐region dynamics and chemistry.

Correlated tunneling in high-order above threshold dissociative ionization of H2

Comprehension of photon-triggered molecular processes is essential in the study of various important topics in physics, chemistry, and biology. Here we propose a correlated tunneling picture to understand the dissociative ionization process of molecules in intense laser fields based on a quantum model developed in the framework of many-body S-matrix theory including nuclear vibrational motion. In this quantum correlation picture, the single ionization of H2 and the subsequent electron-ion recollision-induced dissociation are considered as an entangled correlated process. It enables us to attribute the interference pattern in the joint-energy spectra to combined effects of single-slit diffraction and multi-slit interference of correlated electron-nuclear wave packets in the time domain. Our work opens a new avenue to understanding molecular dissociative ionization processes in external fields.

Extended magenta aurora as revealed by citizen science

During large geomagnetic storms, red auroras are typically observed from low-latitude countries such as Japan. The color arises from a specific emission line of oxygen atoms at high altitudes. However, during the May 10-11th 2024 superstorm, magenta auroras were observed above Japan instead of the typical red. In this study, we demonstrate that the magenta hue is created by a mixture of red (O) and a blue (N2+) aurora at extremely high altitudes. The blue color originates from the N2+ first negative emission band caused by both resonant scattering of the upwelling molecular ions and heavy particle precipitation during the storm. This study is primarily driven by observations from citizen scientists, and confirmed and quantified with observations from spacecraft and modeling techniques. Additionally, we show that high solar activity, terrestrial season, and the preheating of the atmosphere all contribute to the occurrence of magenta aurora. This study showcases the value and richness of citizen science, and we anticipate that such approaches will become increasingly important in the future.

Possibility of identifying 1H-indolylaminium trifluoroacetates with antimicrobial activity by mass spectrometry

The present study proposes a convenient approach to identify a series of novel substituted 1H-indol-5-,6-ylaminium trifluoroacetates with antimicrobial activity based on mass spectral data obtained using direct injection into an ion source at an elevated temperature when the salts decompose with the release of counterions: acids and organic bases – substituted 1H-indolylamines. By the presence of ions with m/z 69, 45, 28, 17 in the spectra, it is judged that the salts are formed by trifluoroacetic acid. Using the available literature data on the mass spectrometry of substituted indoles, aromatic amines, and carboxylic acids, substantiated schemes for the decomposition of molecular ions of organic bases, 1H-indolylamines, are compiled and discussed, in which the mechanism of formation and the structure of fragment ions arising under electron ionization conditions are given. The revealed general, as well as individual for individual representatives with a certain character and place of substitution in the indole bicycle, patterns of behavior of 1H-indolylamine radical ions under conditions of high-temperature mass spectral imaging make it possible to judge their structure and, in general, the structure of 1H-indolylamine trifluoroacetates. The approach used in this work can also be used to prove compounds of a similar group based on the analysis of their mass spectra.

Quantum Chemical Analysis of the Molecular and Fragment Ion Formation of Butyrophenone by High-Electric Field Tunnel Ionization at Atmospheric Pressure.

The molecular ion M+· was observed when the liquid sample of butyrophenone was supplied using atmospheric pressure corona discharge (APCD). In contrast, the vapor supply resulted in the formation of the protonated molecule [M+H]+. The mass spectrum obtained with the liquid supply showed two distinctive fragment ions at m/z 105 and 120, resulting from α-cleavage and McLafferty rearrangement (McLR), respectively. The APCD spectrum showed peaks of M+· and the characteristic two fragment ions that were the same as the field ionization mass spectra of butyrophenone as reported by Chait et al. and Beckey et al. The formation of the molecular and fragment ions strongly indicated that high-electric field tunnel ionization (HEFTI) occurs by the HEF strength exceeding 108 V/m at the tip of the corona needle in APCD. The charge and spin density distributions of the molecular and fragment ions were analyzed by quantum chemical calculations using time-dependent density functional theory (TDDFT) and natural bond orbital (NBO) analysis.

Cold Molecular Ions via Autoionization below the Dissociation Limit.

Several diatomic transition metal oxides, rare-earth metal oxides, and fluorides have the unusual property that their bond dissociation energy is larger than their ionization energy. In these molecules, bound levels above the ionization energy can be populated via strong, resonant transitions from the ground state. The only relevant decay channel of these levels is autoionization; predissociation is energetically not possible and radiative decay is many orders of magnitude slower. Starting from translationally cold neutral molecules, translationally cold molecular ions can thus be produced with very high efficiency. By populating bound levels just above the ionization energy, internally cold molecular ions, exclusively occupying the lowest rotational level, are produced. This is experimentally shown here for the dysprosium monoxide molecule DyO, for which the lowest bond dissociation energy is determined to be 0.0831(6)eV above the ionization energy.

Adsorption of Polycyclic Aromatics on Crystal Surface of Coordination Cages: Photophysical Properties and Förster Resonance Energy Transfer.

Self-assembly reactions of PdX2 (X- = NO3-, BF4-, ClO4-, ReO4-, PF6-, and CF3SO3-) with 9,10-bis((isoquinolin-5-yloxy)methyl)anthracene (L) in Me2SO give rise to single crystals of coordination cages, [X@Pd2L4]X3, irrespective of X- anions, in high yields. The intracage Pd···Pd distance is significantly sensitive to the nestled X- anion, which can serve as a gauge for recognition of ubiquitous polyatomic anions. One interesting feature is that, via π-π interactions, various polycyclic aromatics (PAs) are characteristically adsorbed on the crystal surface of designed coordination cages with a wall of anthranyl moiety. This unprecedented ensemble system shows an efficient Förster resonance energy transfer (FRET) process from the anthracene (ANT) to pyrene (PYR) via a large degree of spectral overlap between the ANT emission and PYR absorption bands, in contrast to a simple mixture of ANT and PYR.

Structural Phase Transitions of Mg2NiH4 Induced by NiH4 Molecular Ion Distortion and Metal Lattice Deformation under High Pressures.

Experimental observations indicate that pressure treatments transform the monoclinic and orthorhombic low-temperature phases of Mg2NiH4 into an unresolved pseudocubic phase even at room temperatures, resembling the temperature-induced phase transformation of the material. This pressure-induced phase transformation is anticipated to involve deformations of the tetrahedrally bonded NiH4 molecular ion and the metal lattice. However, the precise mechanism underlying this transformation remains unclear. To elucidate this behavior, this study adopted first-principles density functional theory calculations to investigate the effect of applied pressure on the observed phase transition. The results revealed that the phase transition from the low-temperature phases to the pseudocubic phase occurs at approximately 8-9 GPa. Furthermore, at this pressure, the metal lattice deforms into an antifluorite-like structure, and the NiH4 molecular ion undergoes substantial distortion, resulting in the alignment of hydrogen atoms along the crystal axes of the metal lattice. Furthermore, through a comprehensive structural exploration, we successfully identified several tetragonal and orthorhombic models that are energetically more stable than the low-temperature phases at low pressures. These models are potential candidates for elucidating the pseudocubic phase observed in experiments. Overall, our findings are anticipated to enhance the current understanding of the structural changes occurring during pressure and temperature-induced phase transitions.

Comprehensive Data Evaluation Methods Used in Developing the SWGDRUG Mass Spectral Reference Library for Seized Drug Identification.

The mass spectral library of the Scientific Working Group for the Analysis of Seized Drugs (SWGDRUG) is the most comprehensive free reference database of its kind in the world. It provides reliable mass spectra for identification of seized drugs, their metabolites, and related forensic compounds when using gas chromatography/mass spectrometry (GC/MS). The SWGDRUG library (version 3.13) contains spectra for 3598 compounds. All spectra are evaluated by the Mass Spectrometry Data Center (MSDC) at the National Institute of Standards and Technology (NIST). Over the past few years, new evaluation methods aided by improved software have been developed. First, all chemical information, such as chemical structure and name, is confirmed. Second, the product ions in each spectrum are verified to match the compound structure using the NIST MS Interpreter software tool. Subsequently, the mass spectra are compared to the same or similar compounds across six different mass spectral reference libraries using three distinct library search methods. Additionally, the NIST Artificial Intelligence Retention Indices (AIRI) software is used to help confirm the corresponding compounds of spectra, especially for those without molecular ions. Low-quality and incorrect spectra are rejected for inclusion in the library.

Simultaneous Probing of Electron Density and Temperature Dynamics Inside Air Plasma with Intense Terahertz Pulses

AbstractAir plasma induced by ultrafast laser pulses is an extraordinary source of electromagnetic waves, emitting microwave, terahertz (THz) radiation, and cavityless lasing in the near‐infrared and visible ranges. The temporal dynamics of the electron density have been revealed by optical pump‐probe techniques, while the evolution of the electron temperature remains elusive due to a lack of suitable methods. Here, it is demonstrated that the intense THz‐field‐enhanced fluorescence emission from the excited molecules of nitrogen is a novel tool that allows to explore the complex dynamics of the plasma density and electron temperature simultaneously. Two relaxation times of electrons in air plasma are observed and interpreted as a competition between the excitation of a triplet state by laser or THz‐field‐heated electrons and the dissociative recombination of nitrogen molecular ions. Based on the theoretical simulations, the tens of picoseconds relaxation process is attributed to the ultrafast temperature decrease, while the longer relaxation in the range of hundreds of picoseconds is ascribed to the decay of electron density. The temporal relaxation of both the electron density and temperature revealed by applying an intense THz field provides further insights into the laser‐air plasma interaction and will benefit the engineering of this exceptional source.

Bacteria from the Amycolatopsis genus associated with a toxic bird secrete protective secondary metabolites

Uropygial gland secretions of birds consist of host and bacteria derived compounds and play a major sanitary and feather-protective role. Here we report on our microbiome studies of the New Guinean toxic bird Pachycephala schlegelii and the isolation of a member of the Amycolatopsis genus from the uropygial gland secretions. Bioactivity studies in combination with co-cultures, MALDI imaging and HR-MS/MS-based network analyses unveil the basis of its activity against keratinolytic bacteria and fungal skin pathogens. We trace the protective antimicrobial activity of Amycolatopsis sp. PS_44_ISF1 to the production of rifamycin congeners, ciromicin A and of two yet unreported compound families. We perform NMR and HR-MS/MS studies to determine the relative structures of six members belonging to a yet unreported lipopeptide family of pachycephalamides and of one representative of the demiguisins, a new hexapeptide family. We then use a combination of phylogenomic, transcriptomic and knock-out studies to identify the underlying biosynthetic gene clusters responsible for the production of pachycephalamides and demiguisins. Our metabolomics data allow us to map molecular ion features of the identified metabolites in extracts of P. schlegelii feathers, verifying their presence in the ecological setting where they exert their presumed active role for hosts. Our study shows that members of the Actinomycetota may play a role in avian feather protection.

Theoretical study on the spectrum properties of tellurium iodide cation

The molecular potential energy function plays an important role in many fields. In this paper, the icMRCI + Q method was utilized to compute the potential energy and dipole moments for 22 Λ-S states and 51 Ω states of the TeI+ system. Two basis sets (AVQZ-PP and AWCVQZ-PP) were employed to compute the TeI+ system, with the results indicating that the AVQZ-PP basis set yielded more accurate results. Therefore, all calculations in this paper are based on this basis set. Furthermore, to ensure the accuracy of the results, a comparison was conducted on the spectral parameters of the ground state and two excited states of the molecular ion within the same main group. Given the significant impact of spin–orbit coupling, as indicated by the calculated SO matrix elements, our discussion will predominantly center on the avoidance of crossovers in the Ω states. Finally, the Franck-Condon factors, Einstein coefficients and radiative lifetime between these two states were calculated from the data of the transition between the X3Σ0+-↔11Σ0++ of the TeI+ molecule.

Predicting Collision-Induced-Dissociation Tandem Mass Spectra (CID-MS/MS) Using Ab Initio Molecular Dynamics.

Compound identification is at the center of metabolomics, usually by comparing experimental mass spectra against library spectra. However, most compounds are not commercially available to generate library spectra. Hence, for such compounds, MS/MS spectra need to be predicted. Machine learning and heuristic models have largely failed except for lipids. Here, quantum chemistry software can be used to predict mass spectra. However, quantum chemistry predictions for collision induced dissociation (CID) mass spectra in LC-MS/MS are rare. We present the CIDMD (Collision-Induced Dissociation via Molecular Dynamics) framework to model CID-based MS/MS spectra. It uses first-principles molecular dynamics (MD) to simulate the physical process of molecular collisions in CID tandem mass spectrometry. First, molecular ions are constructed at specific protonation sites. Using density functional theory, these protonated ions are targeted by argon collider gas atoms at user-specified velocities. Subsequent bond breakages are simulated over time for at least 1,000 fs. Each simulation is repeated multiple times from various collisional directions. Fragmentations are accumulated over those repeated collisions to generate CIDMD in silico mass spectra. Twelve small metabolites (<205 Da) were selected to test the accuracy of this framework in comparison to experimental MS/MS spectra. When testing different protomers, collider velocities, number of simulations, simulation time and impact factor b cutoffs, we yielded 261 predicted mass spectra. These in silico spectra resulted in entropy similarity scores of an average 624 ± 189 for all 261 spectra compared to their corresponding experimental spectra, which improved to 828 ± 77 when using optimal parameters of the most probable protomers for 12 molecules. With increasing molecular mass, higher velocities achieved better results. Similarly, different protomers showed large differences in fragmentation; hence, with increasing numbers of protomers and tautomers, the average CIDMD prediction accuracy decreased. Mechanistic details showed that specific fragment ions can be produced from different protomers via multiple fragmentation pathways. We propose that CIDMD is a suitable tool to predict mass spectra of small metabolites like produced by the gut microbiome.