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Low-energy (0–14 eV) resonance electron interaction and fragment species produced by dissociative electron attachment (DEA) for enantiomeric forms of glutamic acid (Glu) are studied under gas-phase conditions by means of DEA spectroscopy and density functional theory calculations. Contrary to a series of amino acids studied earlier employing the DEA technique, the most abundant species are not associated with the elimination of a hydrogen atom from the parent molecular negative ion. Besides this less intense closed-shell [Glu – H]– fragment, only two mass-selected negative ions, [Glu – 19]– and [Glu – 76]–, are detected within the same electron energy region, with the yield maximum observed at around 0.9 eV. This value matches well the energy of vertical electron attachment into the lowest normally empty π* COOH molecular orbital of Glu located at 0.88 eV according to the present B3LYP/6-31G(d) calculations. Although the detection of asymmetric DEA properties a priori is not accessible under the present experimental conditions, "chirality non-conservation" can be associated with some decay channels. Evidently, the measured spectra for the L- and D-forms are found to be identical, the results, nevertheless, being of interest for the forthcoming experiments utilizing spin-polarized electron beam as a chiral factor in the framework of conventional DEA technique. [ABSTRACT FROM AUTHOR]

Simulating electrolyte–electrode systems poses challenges due to the need to account for the electrode's response to ion movements in order to maintain a constant electrode potential, which slows down the simulations. To circumvent this, computationally more efficient constant charge (CC) simulations are sometimes employed. However, the accuracy of CC simulations in capturing the behavior of electrolyte–electrode systems remains unclear, especially for microporous electrodes. Herein, we consider electrolyte-filled slit nanopores and systematically analyze the in-pore ion structure and diffusivity using CC and constant potential simulations. Our results indicate that CC simulations provide comparable pore occupancies at high bulk ion densities and for highly charged pores, but they fail to accurately describe the ion structure and dynamics, particularly in quasi-2D (single-layer) pores and at low ion densities. We attribute these results to the superionic state emerging in conducting nanoconfinement and its interplay with excluded volume interactions. [ABSTRACT FROM AUTHOR]

Motivated by the multiferroic effects and quantum magnetization plateaus in the skew chain antiferromagnets T 2 V 2 O 7 (T = Ni, Co), we have conducted a detailed density function theoretical study on Co 2 V 2 O 7. The results show that the nearest-neighbor interchain interaction (J 3 / k B = − 35.57 K) is not much greater than the intrachain interactions (J 1 / k B = − 19.54 K and J 2 / k B = 27.55 K), showing the absence of interchain dimerization of the Co ions. This indicates that the "dimer+monomer" model used for Ni 2 V 2 O 7 [Cao et al., Phys. Rev. B 106, 184409 (2022)] is no longer applicable to Co 2 V 2 O 7. Finally, the exact diagonalization of spin Hamiltonian, including anisotropic exchanges, produces the experimentally observed 1/2 and 3/4 magnetization plateaus. [ABSTRACT FROM AUTHOR]

Motivated by the multiferroic effects and quantum magnetization plateaus in the skew chain antiferromagnets T 2 V 2 O 7 (T = Ni, Co), we have conducted a detailed density function theoretical study on Co 2 V 2 O 7. The results show that the nearest-neighbor interchain interaction (J 3 / k B = − 35.57 K) is not much greater than the intrachain interactions (J 1 / k B = − 19.54 K and J 2 / k B = 27.55 K), showing the absence of interchain dimerization of the Co ions. This indicates that the "dimer+monomer" model used for Ni 2 V 2 O 7 [Cao et al., Phys. Rev. B 106, 184409 (2022)] is no longer applicable to Co 2 V 2 O 7. Finally, the exact diagonalization of spin Hamiltonian, including anisotropic exchanges, produces the experimentally observed 1/2 and 3/4 magnetization plateaus. [ABSTRACT FROM AUTHOR]

To efficiently generate H − ions from positive atomic or molecular hydrogen beams injected onto a solid surface, it has been suggested to use a material with a low-work function as the target material. However, it is not clear under what conditions the most efficient H − production is realized for incident beam parameters or reflection angles. Therefore, we studied the interaction between low-energy atomic and molecular hydrogen beams (less than 1 keV/nucleon) with a low-work function electride 12CaO ⋅ 7 A l 2 O 3 (C12A7). The production ratio of H − to H + ions from the C12A7 electride was much higher than Mo targets with higher work functions, especially at smaller incident and smaller reflection angles. The H − to H + production ratio slightly increased as the incident energies were decreased, but there was no significant difference between the electride and Mo targets. These results indicate that smaller incident angles and lower beam energies of the incident hydrogen beam are favorable for the enhancement of the production ratio of H − to H + ions in C12A7. The higher production ratio appeared at the vertical beam energies less than on the order of 100 eV, where quantum mechanical processes may become important. [ABSTRACT FROM AUTHOR]

In this work, we performed static density functional theory calculations and ab initio metadynamics simulations to systematically investigate the association mechanisms and dynamic structures of four kinds of ion pairs that could be formed before the nucleation of CaCO3. For Ca2+– H C O 3 − and Ca2+– C O 3 2 − pairs, the arrangement of ligands around Ca2+ evolves between the six-coordinated octahedral structure and the seven-coordinated pentagonal bipyramidal structure. The formation of ion pairs follows an associative ligand substitution mechanism. Compared with H C O 3 − , C O 3 2 − exhibits a stronger affinity to Ca2+, leading to the formation of a more stable precursor phase in the prenucleation stage, which promotes the subsequent CaCO3 nucleation. In alkaline environments, excessive OH− ions decrease the coordination preference of Ca2+. In this case, the formation of Ca(OH)+– C O 3 2 − and Ca(OH)2– C O 3 2 − pairs favors the dissociative ligand substitution mechanism. The inhibiting effects of OH− ion on the CaCO3 association can be interpreted from two aspects, i.e., (1) OH− neutralizes positive charges on Ca2+, decreases the electrostatic interactions between Ca2+ and C O 3 2 − , and thus hinders the formation of the CaCO3 monomer, and (2) OH− decreases the capacity of Ca2+ for accommodating O, making it easier to separate Ca2+ and C O 3 2 − ions. Our findings on the ion association behaviors in the initial stage of CaCO3 formation not only help scientists evaluate the impact of ocean acidification on biomineralization but also provide theoretical support for the discovery and development of more effective approaches to manage undesirable scaling issues. [ABSTRACT FROM AUTHOR]

The surfaces of many minerals are covered by naturally occurring cations that become partially hydrated and can be replaced by hydronium or other cations when the surface is exposed to water or an aqueous solution. These ion exchange processes are relevant to various chemical and transport phenomena, yet elucidating their microscopic details is challenging for both experiments and simulations. In this work, we make a first step in this direction by investigating the behavior of the native K+ ions at the interface between neat water and the muscovite mica (001) surface with ab-initio-based machine learning molecular dynamics and enhanced sampling simulations. Our results show that the desorption of the surface K+ ions in pure ion-free water has a significant free energy barrier irrespective of their local surface arrangement. In contrast, facile K+ diffusion between mica's ditrigonal cavities characterized by different Al/Si orderings is observed. This behavior suggests that the K+ ions may favor a dynamic disordered surface arrangement rather than complete desorption when exposed to deionized water. [ABSTRACT FROM AUTHOR]

Redox potentials depend on the nature of the solvent/electrolyte through the solvation energies of the ionic solute species. For concentrated electrolytes, ion solvation may deviate significantly from the Born model predictions due to ion pairing and correlation effects. Recently, Ghorai and Matyushov [J. Phys. Chem. B 124, 3754–3769 (2020)] predicted, on the basis of linear response theory, an anomalous trend in the solvation energies of room temperature ionic liquids, with deviations of hundreds of kJ/mol from the Born model for certain size solutes/ions. In this work, we computationally evaluate ionic solvation energies in the prototypical ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM/BF4), to further explore this behavior and benchmark several of the approximations utilized in the solvation energy predictions. For comparison, we additionally compute solvation energies within acetonitrile and molten NaCl salt to illustrate the limiting behavior of purely dipolar and ionic solvents. We find that the overscreening effect, which results from the inherent charge oscillations of the ionic liquid, is substantially reduced in magnitude due to screening from the dipoles of the molecular ions. Therefore, for the molten NaCl salt, for which the ions do not have permanent dipoles, modulation of ionic solvation energies from the overscreening effect is most significant. The conclusion is that ionic liquids do indeed exhibit unique solvation behavior due to peak(s) in the electrical susceptibility caused by the ion shell structure; redox potential shifts for BMIM/BF4 are of more modest order ∼0.1 V, but may be larger for other ionic liquids that approach molten salt behavior. [ABSTRACT FROM AUTHOR]

The proton transport in one-dimensional (1D) confined water chains has been extensively studied as a model for ion channels in cell membrane and fuel cell. However, the mechanistic understanding of the proton transfer (PT) process in 1D water chains remains incomplete. In this study, we demonstrate that the two limiting structures of the hydrated excess proton, H5O2+ (Zundel) and H3O+ (linear H7O3+), undergo a change in dominance as the water chain grows, causing two co-existing and opposing PT mechanisms. Specifically, H5O2+ is stable in the middle of the chain, whereas H3O+ serves as a transition state (TS). Except for this region, H3O+ is stabilized while H5O2+ serves as a TS. The interaction analysis shows that the electrostatic interaction plays a crucial role in the difference in PT mechanisms. Our work fills a knowledge gap between the various PT mechanisms reported in bulk water and long 1D water chains, contributing to a deeper understanding of biological ion channels at the atomic level. [ABSTRACT FROM AUTHOR]

Rovibrational levels of low-lying electronic states of the gas-phase, diatomic molecules, PtH+ and PtH−, are computed on potential-energy functions obtained by using a hybrid spin–orbit configuration-interaction procedure. PtH− has a well-separated Σ 0 + + 1 ground state, while the first two electronic states of PtH+ ( Σ 0 + + 1 and 3Δ3) are nearly degenerate. Combining the experimental photoelectron (PE) spectra of PtH− with theoretical photodetachment spectroscopy leads to an improved value for the electron affinity of PtH, EA(PtH) = (1.617 ± 0.015) eV. When PtH− is a product of photodissociation of PtHCO2−, its PE spectrum is broad because of rotational excitation. Temperature-dependent thermodynamic functions and thermochemistry of dissociation are computed from the theoretical energy levels. Previously published energetic quantities for PtH+ and PtH− are revised. The ground 1Σ+ term of PtH+ is not well described using single-reference theory. [ABSTRACT FROM AUTHOR]

Proflavine, a fluorescent cationic dye with strong absorption in the visible, has been proposed as a potential contributor to diffuse interstellar bands (DIBs). To investigate this hypothesis, it is essential to examine the spectra of cold and isolated ions for comparison. Here, we report absorption spectra of proflavine ions, trapped in a liquid-nitrogen-cooled ion trap filled with helium-buffer gas, as well as fluorescence spectra to provide further information on the intrinsic photophysics. We find absorption- and fluorescence-band maxima at 434.2 ± 0.1 and 434.7 ± 0.3 nm, corresponding to a Stokes shift of maximum 48 cm−1, which indicates minor differences between ground-state and excited-state geometries. Based on time-dependent density functional theory, we assign the emitting state to S2 as its geometry closely resembles that of S0, whereas the S1 geometry differs from that of S0. As a result, simulated spectra involving S1 exhibit long Franck-Condon progressions, absent in the experimental spectra. The latter displays well-resolved vibrational features, assigned to transitions involving in-plane vibrational modes where the vibrational quantum number changes by one. Dominant transitions are associated with vibrations localized on the NH2 moieties. Experiments repeated at room temperature yield broader spectra with maxima at 435.5 ± 1 nm (absorption) and 438.0 ± 1 nm (fluorescence). We again conclude that prevalent fluorescence arises from S2, i.e., anti-Kasha behavior, in agreement with previous work. Excited-state lifetimes are 5 ± 1 ns, independent of temperature. Importantly, we exclude the possibility that a narrow DIB at 436.4 nm originates from cold proflavine cations as the band is redshifted compared to our absorption spectra. [ABSTRACT FROM AUTHOR]

Numerous electrochemistry reactions require the precise calculation of the ion solvation energy. Despite the significant progress in the first-principles calculations for crystals and defect formation energies for solids, the liquid system free energy calculations still face many challenges. Ion solvation free energies can be calculated via different semiempirical ways, e.g., using implicit solvent models or cluster of explicit molecule models; however, systematically improving these models is difficult due to their lack of a solid theoretical base. A theoretically sound approach for calculating the free energy is to use thermodynamic integration. Nevertheless, owing to the difficulties of self-consistent convergence in first-principles calculations for unphysical atomic configurations, the computational alchemy approach has not been widely used for first-principles calculations. This study proposes a general approach to use first-principles computational alchemy for calculating the ion solvation energy. This approach is also applicable for other small molecules. The calculated ion solvation free energies for Li+, Na+, K+, Be2+, Mg2+, and Ca2+ are close to the experimental results, and the standard deviation due to molecular dynamics fluctuations is within 0.06 eV. [ABSTRACT FROM AUTHOR]

Rovibrational levels of low-lying electronic states of the gas-phase, diatomic molecules, PtH+ and PtH−, are computed on potential-energy functions obtained by using a hybrid spin–orbit configuration-interaction procedure. PtH− has a well-separated Σ 0 + + 1 ground state, while the first two electronic states of PtH+ ( Σ 0 + + 1 and 3Δ3) are nearly degenerate. Combining the experimental photoelectron (PE) spectra of PtH− with theoretical photodetachment spectroscopy leads to an improved value for the electron affinity of PtH, EA(PtH) = (1.617 ± 0.015) eV. When PtH− is a product of photodissociation of PtHCO2−, its PE spectrum is broad because of rotational excitation. Temperature-dependent thermodynamic functions and thermochemistry of dissociation are computed from the theoretical energy levels. Previously published energetic quantities for PtH+ and PtH− are revised. The ground 1Σ+ term of PtH+ is not well described using single-reference theory. [ABSTRACT FROM AUTHOR]

For many years, the recombination of excited ions of argon, Ar + ( P 1 / 2 2 ) , has been assumed negligible under ambient conditions as compared to the recombination of ground-state ions, Ar + ( P 3 / 2 2 ). This opinion was confronted with detailed experimental results that seem to clearly support it. Here, we propose a new interpretation in light of our recent calculations, which shows that the recombination efficiency is comparable for both fine-structure states. Noteworthily, in our model leading to a picture consistent with the experiment, residual dimer ions emerge from A r + ( P 1 / 2 2 ) due to non-adiabatic dynamics effects and interplay in measured data. [ABSTRACT FROM AUTHOR]

We investigate the collapse and expansion dynamics of a linear polyelectrolyte (PE) with hydrodynamic interactions. Using dissipative particle dynamics with a bead–spring PE model, long-range electrostatics, and explicit ions, we examine how the timescales of collapse tcol and expansion texp depend on the chain length N and obtain scaling relationships tcol ∼ Nα and texp ∼ Nβ. For neutral polymers, we derive values of α = 0.94 ± 0.01 and β = 1.97 ± 0.10. Interestingly, the introduction of electrostatic interaction markedly shifts α to α ≈ 1.4 ± 0.1 for salt concentrations within c = 10−4 to 10−2 M. A reduction in the ion-to-monomer size ratio noticeably reduces α. On the other hand, the expansion scaling remains approximately constant, β ≈ 2, regardless of the salt concentration or ion size considered. We find β > α for all conditions considered, implying that expansion is always slower than collapse in the limit of long polymers. This asymmetry is explained by distinct kinetic pathways of collapse and expansion processes. [ABSTRACT FROM AUTHOR]

Various charged thorium ions such as singly charged, doubly charged, and triply charged thorium ions trapped in the ion trap can be used to excite the Th-229 first nuclear excited state via the electronic bridge process. We present an integration of a linear ion trap with a time-of-flight mass spectrometer to investigate trapped Th-232 ions. Various charged thorium ions are produced by laser ablation and dynamically loaded into the ion trap. After sufficient collisional cooling, thorium ions are extracted along one of the radial directions for time-of-flight mass spectrometry by rapidly quenching the trapping potential and applying high-voltage extracting pulses. The charge states of thorium ions are identified and the maximum mass resolutions of thorium ions reach ∼100 with initial 300 K collisional cooling. The velocity distributions of ablated various charged thorium ions are measured, and the results agree well with Monte Carlo simulation. Lifetimes of thorium ions are determined to be a few tens of seconds in the ion trap, which are helpful for further spectroscopic studies of Th-229 nuclear transition. [ABSTRACT FROM AUTHOR]

Nanopore/pillar formation on a Ge substrate can be induced by ion irradiation, which activates the ion beam sputtering and self-organization of point defects. Considering that the size and morphology of nanostructures are dependent on damage production, the irradiation parameters significantly affect nanostructuring. Here, the projected range of incident ions was selected as a parameter to be investigated. The projected range was modified by adding an Au buffer layer on the surface of the substrate, enabling the ions to stop in a shallower layer. The experimental results showed that the deposited Au layer affected the size and morphology of the nanostructures produced by ion irradiation. As a unique morphology, network-like structures were observed on the Au-deposited substrates. These structures were larger than ordinary porous structures. [ABSTRACT FROM AUTHOR]

Molecular cluster ions, which are stored in an electromagnetic trap under ultra-high vacuum conditions, undergo blackbody infrared radiative dissociation (BIRD). This process can be simulated with master equation modeling (MEM), predicting temperature-dependent dissociation rate constants, which are very sensitive to the dissociation energy. We have recently introduced a multiple-well approach for master equation modeling, where several low-lying isomers are taken into account. Here, we experimentally measure the BIRD of CO4●–(H2O)1,2 and model the results with a slightly modified multiple-well MEM. In the experiment, we exclusively observe loss of water from CO4●–(H2O), while the BIRD of CO4●–(H2O)2 leads predominantly to loss of carbon dioxide, with water loss occurring to a lesser extent. The MEM of two competing reactions requires empirical scaling factors for infrared intensities and the sum of states of the loose transition states employed in the calculation of unimolecular rate constants so that the simulated branching ratio matches the experiment. The experimentally derived binding energies are ΔH0(CO4●––H2O) = 45 ± 3 kJ/mol, ΔH0(CO4●–(H2O)–H2O) = 41 ± 3 kJ/mol, and ΔH0(CO2–O2●–(H2O)2) = 37 ± 3 kJ/mol. Quantum chemical calculations on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVDZ level, corrected for the basis set superposition error, yield binding energies that are 2–5 kJ/mol higher than experiment, within error limits of both experiment and theory. The relative activation energies for the two competing loss channels are as well fully consistent with theory. [ABSTRACT FROM AUTHOR]

Resonant electron capture by aza and diaza derivatives of phenanthrene (7,8-benzoquinoline and 1,10-phenanthroline) and anthracene (acridine and phenazine) at incident free electron energies (Ee) in the range of 0–15 eV was studied. All compounds except 7,8-benzoquinoline form long-lived molecular ions (M−) at thermal electron energies (Ee ∼ 0 eV). Acridine and phenazine also form such ions at epithermal electron energies up to Ee = 1.5–2.5 eV. The lifetimes (τa) of M− with respect to electron autodetachment are proportional to the extent of aza-substitution and increase on going from molecules with bent geometry of the fused rings (azaphenanthrenes) to linear isomers (azaanthracenes). These regularities are due to an increase in the adiabatic electron affinities (EAa) of the molecules. The EAa values of the molecules under study were comprehensively assessed based on a comparative analysis of the measured τa values using the Rice–Ramsperger–Kassel–Marcus theory, the electronic structure analysis using the molecular orbital approach, as well as the density functional calculations of the total energy differences between the molecules and anions. The only fragmentation channel of M− ions from the compounds studied is abstraction of hydrogen atoms. When studying [M–H]− ions, electron autodetachment processes were observed, the τa values were measured, and the appearance energies were determined. A comparative analysis of the gas-phase acidity of the molecules and the EAa values of the [M–H]· radicals revealed their proportionality to the EAa values of the parent molecules. [ABSTRACT FROM AUTHOR]

Connexin hemichannels were identified as the first members of the eukaryotic large-pore channel family that mediate permeation of both atomic ions and small molecules between the intracellular and extracellular environments. The conventional view is that their pore is a large passive conduit through which both ions and molecules diffuse in a similar manner. In stark contrast to this notion, we demonstrate that the permeation of ions and of molecules in connexin hemichannels can be uncoupled and differentially regulated. We find that human connexin mutations that produce pathologies and were previously thought to be loss-of-function mutations due to the lack of ionic currents are still capable of mediating the passive transport of molecules with kinetics close to those of wild-type channels. This molecular transport displays saturability in the micromolar range, selectivity, and competitive inhibition, properties that are tuned by specific interactions between the permeating molecules and the N-terminal domain that lies within the pore-a general feature of large-pore channels. We propose that connexin hemichannels and, likely, other large-pore channels, are hybrid channel/transporter-like proteins that might switch between these two modes to promote selective ion conduction or autocrine/paracrine molecular signaling in health and disease processes.

Resonant Auger processes provide a unique perspective on electronic interactions and excited vibrational and electronic states of molecular ions. Here, new data are presented on the resonant Auger decay of excited CH3I in the region just below the I 4d−1 ionization threshold. The resonances include the Rydberg series converging to the five spin–orbit and ligand-field split CH3I (I 4d−1) thresholds, as well as resonances corresponding to excitation from the I 4d5/2,3/2 orbitals into the σ* lowest unoccupied molecular orbital. This study focuses on participator decay that populates the lowest lying states of CH3I+, in particular, the X ̃ 2E3/2 and 2E1/2 states, and on spectator decay that populates the lowest-lying (CH3I2+)σ* states of CH3I+. The CH3I (I 4d−1)σ* resonances are broad, and dissociation to CH3 + I competes with the autoionization of the core-excited states. Auger decay as the molecule dissociates produces a photoelectron spectrum with a long progression (up to v3+ ∼ 25) in the C–I stretching mode of the X ̃ 2E3/2 and 2E1/2 states, providing insights into the shape of the dissociative core-excited surface. The observed spectator decay processes indicate that CH3I+ is formed on the repulsive wall of the lower-lying (CH3I2+)σ* potentials, and the photon-energy dependence of the processes provides insights into the relative slopes of the (4d−1)σ* and (CH3I2+)σ* potential surfaces. Data are also presented for the spectator decay of higher lying CH3I (I 4d−1)nl Rydberg resonances. Photoelectron angular distributions for the resonant Auger processes provide additional information that helps distinguish these processes from the direct ionization signal. [ABSTRACT FROM AUTHOR]

We describe an apparatus where many species of ultracold atoms can be simultaneously trapped and overlapped with many species of ions in a Paul trap. Several design innovations are made to increase the versatility of the apparatus while keeping the size and cost reasonable. We demonstrate the operation of a three-dimensional (3D) magneto-optical trap (MOT) of 7Li using a single external cavity diode laser. The 7Li MOT is loaded from an atomic beam, with atoms slowed using a Zeeman slower designed to work simultaneously for Li and Sr. The operation of a 3D MOT of 133Cs, loaded from a 2D MOT, is demonstrated, and provisions for MOTs of Rb and K in the same vacuum manifold exist. We demonstrate the trapping of 7Li+ and 133Cs+ at different settings of the Paul trap and their detection using an integrated time-of-flight mass spectrometer. We present results on low energy neutral–neutral collisions (133Cs–133Cs, 7Li–7Li, and 133Cs–7Li collisions) and charge–neutral collisions (133Cs+–133Cs and 7Li+–7Li collisions). We show evidence of sympathetic cooling of 7Li+ (133Cs+) due to collisions with the ultracold 7Li (133Cs). [ABSTRACT FROM AUTHOR]

We present a device simulation of lead-halide perovskite-based thin film transistors (TFTs) containing mobile charged species to provide physical reasoning for the various experimental reports. We study the output characteristics for a range of scan duration (1/speed), average mobile ion densities, and N- and P-channel TFTs. We then directly compare our results to published data by Zeidell et al. [Adv. Electron. Mater. 4(12), 1800316 (2018)] and show that if the transistor's measurement procedure is such that the ions' effects are apparent, and then, our model can resolve the sign of the mobile ions in their MAPbI3−xClx TFTs (cations) and provide a good estimate of their density (∼1017 cm−3 at 200 k). Interestingly, we find that effects previously associated with channel screening are due to the ion-blocking of the charge extraction and that the incomplete saturation often reported is due to ion-induced channel shortening. Utilizing the same perovskite materials as in solar cells would allow researchers to improve their understanding of the mechanisms governing solar photovoltaics and improve their performance. [ABSTRACT FROM AUTHOR]

In this work, the electrostatic response of an electrolyte solution to a spherical ion is studied with a Gaussian field theory. In order to capture the ionic correlation effect in concentrated solutions, the bulk dielectric response function is described by a two-Yukawa response function. The modified response function of the solution is solved analytically in the spherical geometry, from which the induced charge density and the electrostatic energy are also derived analytically. Comparisons with results for small ions in electrolyte solutions from the hyper-netted chain theory demonstrate the validity of the Gaussian field theory. [ABSTRACT FROM AUTHOR]

Molecular simulations serve as indispensable tools for investigating the kinetics and elucidating the mechanism of hindered ion transport across nanoporous membranes. In particular, recent advancements in advanced sampling techniques have made it possible to access translocation timescales spanning several orders of magnitude. In our prior study [Shoemaker et al., J. Chem. Theory Comput. 18, 7142 (2022)], we identified significant finite size artifacts in simulations of pressure-driven hindered ion transport through nanoporous graphitic membranes. We introduced the ideal conductor model, which effectively corrects for such artifacts by assuming the feed to be an ideal conductor. In the present work, we introduce the ideal conductor dielectric model (Icdm), a generalization of our earlier model, which accounts for the dielectric properties of both the membrane and the filtrate. Using the Icdm model substantially enhances the agreement among corrected free energy profiles obtained from systems of varying sizes, with notable improvements observed in regions proximate to the pore exit. Moreover, the model has the capability to consider secondary ion passage events, including the transport of a co-ion subsequent to the traversal of a counter-ion, a feature that is absent in our original model. We also investigate the sensitivity of the new model to various implementation details. The Icdm model offers a universally applicable framework for addressing finite size artifacts in molecular simulations of ion transport. It stands as a significant advancement in our quest to use molecular simulations to comprehensively understand and manipulate ion transport processes through nanoporous membranes. [ABSTRACT FROM AUTHOR]

Most of the available data on diffusion in natural clayey rocks consider tracer diffusion in the absence of a salinity gradient despite the fact that such gradients are frequently found in natural and engineered subsurface environments. To assess the role of such gradients on the diffusion properties of clayey materials, through-diffusion experiments were carried out in the presence and absence of a salinity gradient using salt-diffusion and radioisotope tracer techniques. The experiments were carried out with vermiculite samples that contained equal proportions of interparticle and interlayer porosities so as to assess also the role played by the two types of porosities on the diffusion of water and ions. Data were interpreted using both a classical Fickian diffusion model and with a reactive transport code, CrunchClay that can handle multi-porosity diffusion processes in the presence of charged surfaces. By combining experimental and simulated data, we demonstrated that (i) the flux of water diffusing through vermiculite interlayer porosity was minor compared to that diffusing through the interparticle porosity, and (ii) a model considering at least three types of porous volumes (interlayer, interparticle diffuse layer, and bulk interparticle) was necessary to reproduce consistently the variations of neutral and charged species diffusion as a function of salinity gradient conditions.

Non-specific amplification (NSA, amplification in the absence of a target analyte) in bioanalytical rolling circle amplification (RCA) assays, especially those involving pre-synthesized circular DNA (cDNA), affects its analytical sensitivity. Despite extensive development of RCA-based bioanalytical methods, the NSA in RCA remains uncharacterized in terms of its magnitude or origin. NSA may originate from inefficient ligation or succeeding cDNA purification steps. This study comprehensively quantifies NSA across several ligation and digestion techniques for the first time since the innovation of RCA. To quantify the NSA in RCA, cDNAs were prepared using self-annealing, splint-padlock, or cohesive end ligations. The cDNAs were then subjected to nine different exonuclease digestion steps and quantified for NSA under linear as well as hyperbranched RCA conditions. We investigated buffer compositions, divalent ion concentrations, single or dual enzyme digestion, cohesive end lengths, and splint lengths. The optimized conditions successfully mitigated absolute NSA by 30–100-fold and relative NSA (normalized against primer-assisted RCA) to ∼5%. Besides understanding the mechanistic origin of NSA, novel aspects of enzyme–substrate selectivity, buffer composition, and the role of divalent ions were discovered. With increasing bioanalytical RCA applications, this study will help standardize NSA-free assays. [ABSTRACT FROM AUTHOR]

The doping of photocatalytic La5Ti2AgO7S5 particles with aliovalent metal cations was investigated. The incorporation of lower-valence Al3+ cations at Ti4+ sites improved the photocatalytic hydrogen evolution activity. In addition, the anodic photocurrent during oxygen evolution was increased upon adding higher-valence Ta5+ ions. The effect of doping on the carrier density in the photocatalytic particles was also examined in this work. [ABSTRACT FROM AUTHOR]

The first dispiro orthoester via a spiroacetal oxo-carbenium ion is presented. Oxidative dearomatization of phloretic esters results in a bifunctional electrophilic spiroacetal oxo-carbenium ion, which undergoes a double nucleophilic addition by diol delivering a range of unusual dispiro-orthoesters with an excellent diversity. [ABSTRACT FROM AUTHOR]

Exploring the connections between the ion substitution of a material, its crystal structure, and its performance in applications is a regular task in synthetic chemistry. However, there still remain major challenges in the substitution of polyanionic groups for single ions. Herein, a strategy of channel species substitution of single anions by polyanionic groups in a zeotype rigid framework to design a new deep-ultraviolet nonlinear zincophosphate, {[Li3Na3(SiF6)]Cs2}[(ZnPO4)6], and tune physicochemical properties was proposed. [ABSTRACT FROM AUTHOR]

Heterogeneous dual‐site electrocatalysts are emerging cutting‐edge materials for efficient electrochemical water splitting. However, the corresponding oxygen evolution reaction (OER) mechanism on these materials is still unclear. Herein, based on a series of in situ spectroscopy experiments and density function theory (DFT) calculations, a new heterogeneous dual‐site O−O bridging mechanism (DSBM) is proposed. This mechanism is to elucidate the sequential appearance of dual active sites through in situ construction (hybrid ions undergo reconstruction initially), determine the crucial role of hybrid dual sites in this mechanism (with Ni sites preferentially adsorbing hydroxyls for catalysis followed by proton removal at Fe sites), assess the impact of O−O bond formation on the activation state of water (inducing orderliness of activated water), and investigate the universality (with Co doping in Ni(P4O11)). Under the guidance of this mechanism, with Fe−Ni(P4O11) as pre‐catalyst, the in situ formed Fe−Ni(OH)2 electrocatalyst has reached a record‐low overpotential of 156.4 mV at current density of 18.0 mA cm−2. Successfully constructed Fe−Ni(P4O11)/Ti uplifting the overall efficacy of the phosphate from moderate to superior, positioning it as an innovative and highly proficient electrocatalyst for OER. [ABSTRACT FROM AUTHOR]

In this work, we analyzed the electrophoretic behavior of a double crossover (DX) DNA motif in various counter ions. The influence of the type and concentration of counter ions on electrophoretic behavior is different for the DX motif compared to a duplex of the same molecular weight. Higher concentrations of divalent ions Mg2+ and Ca2+ in the gel and running buffer reduce the electrophoretic migration of the DX motif. This effect is less pronounced in the monovalent ion Na+ while K+ ion did not have any significant effect on the electrophoretic behavior. [ABSTRACT FROM AUTHOR]

Quantum states decohere through interaction with the environment. Quantum error correction can preserve coherence through active feedback wherein quantum information is encoded into a logical state with a high degree of symmetry. Perturbations are detected by measuring the symmetries of the state and corrected by applying gates based on these measurements. To measure the symmetries without perturbing the data, ancillary quantum states are required. Shor error correction uses a separate quantum state for the measurement of each symmetry. Steane error correction maps the perturbations onto a logical ancilla qubit, which is then measured to check several symmetries simultaneously. We experimentally compare Shor and Steane correction of bit flip errors using the Bacon-Shor code implemented in a chain of 23 trapped atomic ions. We find that the Steane method produces fewer errors after a single round of error correction and less disturbance to the data qubits without error correction. [ABSTRACT FROM AUTHOR]

A comparative study of the Gd2O3:Tb and Y2O3:Tb nanoparticles (NPs) was presented to examine the influence of the host lattices on the crystallographic phase, surface characteristics, optical properties, Raman effect, and photoluminescence properties. Cubic shapes Gd2O3:Tb and Y2O3:Tb NPs with an estimated crystalline size of 17 and 11 nm were recorded from the X‐ray diffraction pattern, respectively. Comparative absorption spectra of both oxides NPs were presented to examine the dispersibility, colloidal stability, and optical behavior of the NPs. Energy bandgap values were estimated to monitor the optical characteristics of the metal oxides in the UV/Vis region. Fourier transform infrared was recorded to confirm the surface‐attached water and organic moieties. The Raman spectra of metal oxides were recorded to examine the symmetrical dis‐order and polarizability of the vibrational bands. The ionic radius of the atoms distorts the bond structure resulting in it greatly influenced the vibrational bands of the materials. The emission spectra certified the effective doping of the luminescent Tb3+‐ion in the metal oxide host lattices. Raman spectra and emission spectra validated the crystal symmetry imperfections; subsequently, the efficiency of the Raman active modes and emission transitions was greatly influenced. In a comparative analysis, Y2O3:Tb NPs exhibited higher luminescence intensity in comparison with the Gd2O3:Tb NPs. [ABSTRACT FROM AUTHOR]

A new analytical technique for detection of organic compounds using inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS) is described. Volatile organic compounds (VOCs) were introduced into the collision/reaction cell (CRC), instead of through the ICP ion source, and the molecules were ionised through an ion reaction, induced by collision with the primary ions (Ar+) produced in the ICP. The ionisation characteristics of this new approach were investigated by mass spectrometric analysis of eight VOCs (i.e., benzene, toluene, ethyl acetate, methyl butyrate, ethyl butyrate, pentyl acetate, pyridine, and 2-methylfuran). These molecules were detected as molecular ions (M+), protonated ions ([M + H]+), or deprotonated ions ([M − H]+), demonstrating that soft ionisation was achieved by the present ionisation protocol using ICP-MS/MS. In addition, a volatile selenium-containing organic compound, dimethyl diselenide (Se2(CH3)2), was also analysed to investigate the feasibility of this ionisation protocol to achieve soft and hard ionisation simultaneously. Several Se-related ions such as Se+, SeH+, Se2+, [SeCH3]+, and [Se2CH3]+, together with [Se2(CH3)2]+, were observed, suggesting that while soft ionisation was possible, ion reaction-induced-fragmentation and hard ionisation also occurred. To demonstrate the analytical capability of the present technique, volatile components released from coffee beans were subjected to the present mass spectrometric analysis. Many ion peaks originating from VOCs were detected from the coffee beans. The data obtained here demonstrated that ICP-MS equipped with a CRC can become an effective tool for analyzing both elements and molecules. [ABSTRACT FROM AUTHOR]

Understanding the nature, density, and distribution of structural defects is crucial for tailoring the properties of atomically thin two‐dimensional (2D) materials, which is paramount for advances in nanotechnology. Ion irradiation emerges as a promising technique for defect engineering of single‐atom‐thick materials, due to its high controllability, repeatability, and accuracy. The objective is to provide a comprehensive review elucidating the impact of various irradiation parameters, such as ion mass, energy, fluence, and incident angle, on defect formation in 2D materials. However, the presence of the substrate can significantly influence defect yield and the mechanism of formation due to backscattered ions and sputtered substrate atoms. Hence, a thorough comparison of ion beam‐induced defects in both freestanding (suspended) and supported (on a substrate) 2D materials, with a focus on substrate effects is conducted. Moreover, a detailed analysis of characterization techniques suitable for each scenario will be provided. This work not only contributes to advancing the current understanding of defect formation and evolution in 2D materials during ion beam irradiation but also offers insights into selecting specific parameters for this process to create desired defects in these materials. Consequently, it has the potential to facilitate the design of nanoscale devices with tailored functionality. [ABSTRACT FROM AUTHOR]

The pursuit of high on‐to‐off ratio (IOn/IOff), as one of the important performances for organic electrochemical transistor (OECT) has been ongoing, but to date, limited solutions are available. The interaction between light and matter has been demonstrated as a rich source for advanced electronic applications. However, its potential in IOn/IOff modulation has not been fully explored. Herein, the challenge is addressed through the unique light‐material interplay, which is represented by organic photoelectrochemical transistor (OPECT) gated by photosensitive COF‐LZU1 on mixed‐ligand MOF (COF‐on‐MOF) upon appropriate exposure illumination. Notably, the interplay between light and COF‐on‐MOF can adjust the device physics, optimizing the IOn/IOff to its maximum and enhancing signal transduction. Toward bio‐application, via exonuclease‐assisted cyclic cleavage amplification and hybridization chain reaction, such a device is validated for highly sensitive detection capabilities for human T‐cell lymphotropic virus type II (HTLV‐II) DNA down to 0.003 fM. This study features the possibility of Ag/AgCl‐like photogating of organic transistors via light‐matter interplay. [ABSTRACT FROM AUTHOR]

Transparent electrode‐free light‐emitting devices are presented that exploit electrochemiluminescence (ECL). These devices feature two side‐by‐side noble metal electrodes connected by an ECL active layer. The significance of bulk ion‐transport characteristics is investigated within the ECL active layer in producing uniform planar emission from the device. These characteristics can be enhanced by simply increasing the ECL active layer thickness or adding an ion gel electrolyte layer on top of the ECL active layer. The use of only electrochemically stable noble metal electrodes results in an operational lifetime exceeding 10 h, which is the longest lifetime reported for ECL‐based light‐emitting devices to date. The device structure based on ECL does not require transparent electrodes, allowing for increased flexibility when designing devices for future light‐emitting device applications. [ABSTRACT FROM AUTHOR]

Improvement of the catalytic performance of oxygen evolution reaction (OER) is the key to the large-scale implementation of water electrolysis. Here, we report an efficient strategy to improve the OER activity of Co-based nanocomposite catalysts by adding Fe3+ ions into the electrolyte. The overpotential of cobalt tartrate annealed at 700 °C can be decreased from 360 to 329 mV by introducing 20 ppm Fe3+ into the alkaline electrolyte. Electrochemical measurements indicate that the introduction of Fe3+ can generate more efficient active sites by cooperation with Co species and promote OER kinetics, thus improving electrocatalytic performance. [ABSTRACT FROM AUTHOR]

Plasma‐activated mist (PAM) has seen increasingly widespread applications in areas such as surface disinfection and fog cultivation. The high‐resolution time diagnostics of ns pulse plasma interacting with micron‐sized droplets under high‐humidity conditions is challenging to achieve with existing experimental methods. This paper employs a global model to study the interaction between plasma and droplets, offering a detailed analysis of the plasma's transition from the gas phase to the liquid phase. It was discovered that in high‐humidity environments, hydrated ions become the predominant ion species. These acidic active substances in PAM droplets are the primary factors in the mist's ability to kill bacteria. The paper further examines how variations in droplet size and discharge voltage influence the PAM's activity. [ABSTRACT FROM AUTHOR]

Complex compounds of Cu, Ag, Pd, Pt, and Au with dithizone (diphenylthiocarbazone) were studied by surface-assisted laser desorption/ionization from nanocrystalline silicon. The study demonstrated that all investigated complexes ionize efficiently in the negative ion mode, forming molecular ions and one or more types of fragment ions. The limits of detection for the metal dithizonates were determined. A possibility of coupling laser desorption/ionization mass spectrometry with single drop microextraction for metal detection was explored. Factors affecting the concentration factor were examined, and the optimal conditions for performing single drop microextraction in gold determination were found. The limit of detection for gold is 5 pg/mL. [ABSTRACT FROM AUTHOR]

To study the physicochemical (including adsorption) properties of nanodiamond, it is necessary to reproducibly obtain a carbon surface of an individual particle without metallic impurities of an unknown composition. Such a surface can be obtained through an additional procedure of the deep purification of a commercially available sample. This work is devoted to a study of the composition of non-combustible impurities of detonation diamond nanopowder. Using inductively coupled plasma mass spectrometry, iron and titanium are identified as the main metallic components of the non-combustible residue, the presence of Cr, Ni, Zr, As, and Sb is qualitatively established. The expected composition of the main molecular ions formed on the surface of the non-combustible residue under laser desorption/ionization mass spectrometry conditions is presented. Based on the results of the mass spectrometric analysis, a version of two-stage chemical treatment of detonation diamond nanopowder is proposed, which made it possible to reduce the mass fraction of non-combustible impurities during annealing in air from 2.0 to 0.1%. [ABSTRACT FROM AUTHOR]

We present the angular distribution of the ejected electron for single ionization of He by fast proton impact. A four-body formalism of the three-Coulomb wave is applied to calculate the triple differential cross sections at several impact energies in the scattering, perpendicular and azimuthal planes. Moreover, the three-body formalism of three-Coulomb, two-Coulomb and first Born approximation models has also been used to study the many-body effect on electron emission and the validity of the models. In the three-Coulomb wave model, the final state wave function incorporates distortion due to the three-body mutual Coulombic interaction. In this formalism, we use an uncorrelated and correlated Born initial state, which consists of a plane wave for the incoming projectile times a two-electron bound state wavefunction of the helium atom representing the 1s2(1S) state. But, in the case of the three-body formalism, the initial state wavefunction consists of a long-range Coulomb distortion for the incoming projectile and one active electron of the He atom described by the Roothaan–Hartree–Fock wavefunction. The structure with a single or two peaks with unequal intensity is observed in the angular distributions of the triple differential cross sections for the different kinematic conditions. In addition, the influence of static electron correlations is investigated using different bound state wavefunctions for the ground state of the He target. In the four-body formalism, the present computations are very fast by reducing a nine-dimensional integral to a two-dimensional real integral. Despite the simplicity and speed of the proposed quadrature, the comparison shows that the obtained results are in reasonable agreement with the experiment and are compatible with those of other theories. [ABSTRACT FROM AUTHOR]

In recent years, ion-imprinted polymers have gained significant attention and are extensively utilized owing to their high selectivity toward target ions. For this research, Pb(II) ions were used as the template ions, polyamide-amine dendrimers as the curing agent, epoxy resin as the carrier and combined with ion-imprinting technique in the preparation of Pb(II)-imprinted polymer (Pb(II)-IIP). Systematic adsorption experiments were used to investigate the impact of the adsorbent on the adsorption performance of Pb(II) ions. The composition of the adsorbent was further studied by FT-IR, SEM and other characterization techniques. The maximal adsorption capacity at pH = 5 and T = 318 K was calculated to be 138.8 mg/g. In the coexistence of multiple ions, the Pb(II)-IIP showed high selectivity for Pb(II) adsorption. Pb(II) was still removed at a rate of more than 91% after five cycles of experiments, indicating good reusability. [ABSTRACT FROM AUTHOR]

Removal of sulphur and sulphur compounds from liquid fuel is one of the most critical issues in the environment and energy field due to its widespread use and destructive effects. The aim of this research is the use of a bio-based activated carbon modified with chitosan and Fe ions (AC/Fe/CH) to remove Dibenzothiophene (DBT) from iso-octane as fuel. The properties of this adsorbent were identified using BET, EDX-SEM, and FTIR analyses. The effect of operating parameters including initial concentration (C), adsorbent amount (m), and stirring speed (U) was optimised to reach maximum removal of DBT from iso-octane fuel using RSM methodology. The maximum removal percentage of DBT using AC/Fe/CH was 98.229%, and the optimal conditions were 0.05 g /25 mL of adsorbent, DBT concentration of 149 mg L−1, and stirring speed of 50 rpm. The improvement of adsorption ability is attributed to the modification and creation of iron cations and N+ ions onto the activated carbon surface. DBT is attracted by Fe cations adsorption centre via π-complexation and S-Fe bond and attracted by N+ adsorption centre via electrostatic forces. By analysing the kinetics data with various kinetics models, the result indicated that the pseudo-second-order kinetics model is consistent with the experimental data. The Langmuir model has higher compatibility than other models with the equilibrium data. The Modified activated carbon with chitosan and Fe has the maximum adsorption ability equal to 270 mg g−1. According to the obtained data, the prepared adsorbent (AC/Fe/CH) has the appropriate ability to separate DBT from liquid fuel. [ABSTRACT FROM AUTHOR]

In the research described here, to graft chitosan with the atom transfer radical polymerization (ATRP) method, chitosan acetyl chloride was obtained as a macro-initiator by reacting chitosan with chloracetyl chloride. This macro-initiator was then grafted with monomer [acrylamide (AM) or methacrylamide (MAM), or diacetone acrylamide (DAAM)] in the presence of 2,2'-bipyridine/CuCl as a catalyst system. Structure characterization of all synthesized products was performed with the help of elemental analysis and IR techniques. Additionally, the metal ions (Cu2+, Co2+, Ni2+, and Cd2+) uptake properties of the polymers were determined by atomic absorption spectrophotometry. Metal ion uptake parameters were calculated using various formulas and the results were compared. [ABSTRACT FROM AUTHOR]

Inspired by the "electric jellyfish group" in the ocean, the Ti O H O strong correlation strategy is first proposed and used to construct Hexagon MXene heterojunction for potassium-ions hybrid supercapacitor with high energy density. The adsorption rules and electron transport mechanism of potassium-ions at the Ti O H O interface revealed in this work provide valuable insights into the regulation of ions/electrons at the energy storage interface. [Display omitted] • Inspired by the "electric jellyfish group" in the ocean, the Ti O H O strong correlation strategy is first proposed and used to construct Hexagon MXene heterojunction for potassium-ions hybrid supercapacitor with high energy density. • The Ti O H O interface not only effectively improves the adsorption capacity and adsorption energy of potassium-ions, but also provides a fast channel for electron transport, thus obtaining a remarkable rate performance in neutral electrolyte. • The adsorption rules and electron transport mechanism of potassium-ions at the Ti O H O interface revealed in this work provide valuable insights into the regulation of ions/electrons at the energy storage interface. Potassium-ion hybrid capacitors (PIHC) are considered as ideal large-scale rechargeable energy storage devices due to their low-cost, high-power density and environmental protection. However, a low energy density is the main factor restricting the practical application of PIHC. The interface is formed on the surface of electrode material of PIHC through strong correlation to construct heterojunction, which can significantly improve the performance of ion energy storage. However, how to reveal the influence of the interfacial state of the heterojunction on the adsorption and electron transmission of energy storage ions at the atomic level is still one of the key scientific problems in this field. In this work, metal ion intercalation and microwave-assisted in-situ etching are used to construct the Hexagon MXene Ti 3 C 2 heterojunction with Ti O H O strong correlation. At the interface of heterojunction, Ti O H O highway for electron transmission is developed to improve the rate performance of PIHC. Through experimental and theoretical calculation, the optimum adsorption position and maximum adsorption amount of potassium-ion at the single interface of heterojunction are obtained, and the specific energy density of PIHC is increased. This lays a foundation for the practical application of high-performance soft-package PIHC. [ABSTRACT FROM AUTHOR]

[Display omitted] Developing highly active and durable non-precious metal-based electrocatalysts for the oxygen evolution reaction (OER) is crucial in achieving efficient energy conversion. Herein, we reported a CoNiAl 0.5 O/NF nanofilament that exhibits higher OER activity than previously reported IrO 2 -based catalysts in alkaline solution. The as-synthesized CoNiAl 0.5 O/NF catalyst demonstrates a low overpotential of 230 mV at a current density of 100 mA cm−2, indicating its high catalytic efficiency. Furthermore, the catalyst exhibits a Tafel slope of 26 mV dec−1, suggesting favorable reaction kinetics. The CoNiAl 0.5 O/NF catalyst exhibits impressive stability, ensuring its potential for practical applications. Detailed characterizations reveal that the enhanced activity of CoNiAl 0.5 O/NF can be attributed to the electronic modulation achieved through Al3+ incorporation, which promotes the emergence of higher-valence Ni metal, facilitating nanofilament formation and improving mass transport and charge transfer processes. The synergistic effect between nanofilaments and porous nickel foam (NF) substrate significantly enhances the electrical conductivity of this catalyst material. This study highlights the significance of electronic structures for improving the activity of cost-effective and non-precious metal-based electrocatalysts for the OER. [ABSTRACT FROM AUTHOR]

Synthesis of W nanoparticles by magnetron sputtering combined with gas aggregation operated in Ar suffers from a continuous decrease of the synthesis rate, ceasing in a finite time interval, in the range of minutes to tens of minutes. Experimentally, we noticed that adding small amounts of H2 to Ar (5–20%) increases the synthesis rate, which remains constant over time, at a value dependent on the amount of injected hydrogen. Mass spectrometry investigations revealed, in the hydrogen presence, a dominance of the ArH+ ions over the Ar+ ones, associated also with an increased number of W+ and WH+ species in plasma, sustaining a substantial increase in the nucleation rate. [ABSTRACT FROM AUTHOR]