Charged Clusters Research Articles

Electrochemical Deterioration of a Gold Thin Film in Bicarbonate Solution: Correlative Optical, Nano-Mechanical, and Chemical Considerations.

The electrochemical dissolution of metals in liquid electrolytes is of great concern for various electrochemical technologies. However, it is also the focus for boosting metal recovery processes, e.g., from electronic wastes, one of which is the extraction of gold (Au) using eco-friendly electrolytes. To shed more light on the possibility and improvement of such metal leaching, this work presents the investigation of electrochemical deterioration of a Au nanofilm coated on a silicon (Si) support─ubiquitous materials in electronic components─in aqueous potassium bicarbonate (KHCO3) electrolyte, a solution widely used in food products. In addition to the time-dependent in situ Raman spectra revealing the reduced reflectivity of Au associated with its molecular degradation, the significant role of the electric double layer (EDL) at the metal/electrolyte interface is also indicated. Analyzing surface adhesion maps and force-distance spectra acquired using atomic force microscopy and spectroscopy (AFM/AFS), metal degradation is related to nanoscale worm-shaped reconstructed surface features that act as local sites of reduced refractive index. Complemented by the non-negligible fraction of K observed on the treated Au surfaces using scanning electron microscopy and energy dispersive spectroscopy (SEM/EDS), an electrochemical framework of metal degradation is proposed, depicting the electric-field-induced transport of K+ and H+ ions toward the Au surface regardless of bias polarity and implying the formation of ternary gold hydrides. The consideration of faradic current in the EDL circuit also suggests the occurrence of ternary gold oxides. Such determination is reinforced by the attributability of the polar and electrostatic characteristics of the worm-like features to residual negatively charged anionic clusters of the hydrides and the oxides. The analysis process and the new understanding of metal degradation provide a potential route for inspecting other metal/solution systems.

High stability of charged particle clusters in protoplanetary disks

Context. The initial particle growth in protoplanetary disks is limited by a bouncing barrier at submillimeter wavelengths. Bouncing leads to tribocharging and the electrostatic attraction of tribocharged aggregates may eventually draw them into large clusters. A charge- mediated growth phase allows for the formation of larger entities, namely, clusters of aggregates that are more prone to further particle concentrations, such as the streaming instability. Aims. We aim to quantify the strength of the electrostatic forces. Methods. In laboratory experiments, we used an acoustic trap to levitate small aggregates of tribocharged submm grains. These aggregates spin up within the trap until they lose grains. Thus, we used the centrifugal force as a measure of the local force. Results. Grains are regularly bound strongly to their neighbors. In comparison, the force at ejection can be stronger than the attractive scattering forces of the trap and can therefore be several orders of magnitude larger than expected. We note that these forces are long- ranging, compared to van der Waals forces. Thus, charged aggregates are much more stable than uncharged ones. Conclusions. Particle aggregates in disks might grow to centimeter clusters or larger as tribocharging increases the effective binding forces. This allows for hydrodynamic concentration and planetesimal formation to eventually take place throughout a wide part of the disk.

Characteristics of Bubble Dispersion under Nonuniform Electric Field in an Up-Flow Bubbling System: From Charged Bubble to Charged Bubble Cluster

Characteristics of Bubble Dispersion under Nonuniform Electric Field in an Up-Flow Bubbling System: From Charged Bubble to Charged Bubble Cluster

Reactivity of Atomic Oxygen Radical Anions in Metal Oxide Clusters.

Atomic oxygen radical anion (O⋅-) represents an important type of reactive centre that exists in both chemical and biological systems. Gas-phase atomic clusters can be studied under isolated and well controlled conditions. Studies of O⋅--containing clusters in the gas-phase provide a unique strategy to interpret the chemistry of O⋅- radicals at a strictly molecular level. This review summarizes the research progresses made since 2013 for the reactivity of O⋅- radicals in the atomically precise metal oxide clusters including negatively charged, nanosized, and neutral heteronuclear metal clusters benefitting from the development of advanced experimental techniques. New electronic and geometric factors to control the reactivity and product selectivity of O⋅- radicals under dark and photo-irradiation conditions have been revealed. The detailed mechanisms of O⋅- generation have been discussed for the reaction systems of nanosized and heteroatom-doped metal oxide clusters. The catalytic reactions mediated by the O⋅- radicals in metal clusters have also been successfully established and the microscopic mechanisms about the dynamic generation and depletion of O⋅- radicals have been clearly understood. The studies of O⋅- containing metal oxide clusters in the gas-phase provided new insights into the chemistry of reactive oxygen species in related condensed-phase systems.

From unbound to bound states: Ab initio molecular dynamics of ammonia clusters with an excess electron.

Ab initio molecular dynamics simulations of negatively charged clusters of 2-48 ammonia molecules were performed to elucidate the electronic stability of the excess electron as a function of cluster size. We show that while the electronic stability of finite temperature clusters increases with cluster size, as few as 5-7 ammonia molecules can bind an excess electron, reaching a vertical binding energy slightly less than half of the bulk value for the largest system studied. These results, which are in agreement with previous studies wherever available, allowed us to analyze the excess electron binding patterns in terms of its radius of gyration and shape anisotropy and provide a qualitative interpretation based on a particle-in-a-spherical-well model.

Metastable Evaporation of Molecules from Water Clusters.

We probe the stability of water clusters by means of their metastable decay probability extracted from two-dimensional reflectron time-of-flight mass spectra. Two different methods are used to ionize and potentially excite the clusters and trigger the evaporation: (i) attachment of electrons with near-zero energies, producing negatively charged clusters, and (ii) electron impact ionization, producing protonated (H2O)nH+ clusters. The electron attachment is a soft ionization and therefore provides information about the size distribution of the neutral clusters in the beam due to a very limited amount of post-ionization loss of water molecules. A dependence of metastable fractions on the conditions of neutral clusters production prior to the electron attachment is reported. For the cations, the higher energy electron impact ionization leads to a more extensive metastable loss of water molecules. The results are discussed in the light of neutral cluster excitation energy distributions and, for negative clusters, also in terms of binding energies. The experiments demonstrate clearly the role of the excess electron vs the excess proton in the two different charge states of the clusters around sizes N = 50-55, for which binding energies of the anions are derived from the data.

Water and chloride as allosteric inhibitors in WNK kinase osmosensing.

Osmotic stress and chloride regulate the autophosphorylation and activity of the WNK1 and WNK3 kinase domains. The kinase domain of unphosphorylated WNK1 (uWNK1) is an asymmetric dimer possessing water molecules conserved in multiple uWNK1 crystal structures. Conserved waters are present in two networks, referred to here as conserved water networks 1 and 2 (CWN1and CWN2). Here we show that PEG400 applied to crystals of dimeric uWNK1 induces de-dimerization. Both the WNK1 the water networks and the chloride binding site and are disrupted by PEG400. CWN1 is surrounded by a cluster of pan-WNK-conserved charged residues. Here we mutagenized these charges in WNK3, a highly active WNK isoform kinase domain, and WNK1, the isoform best studied crystallographically. Mutation of E314 in the Activation Loop of WNK3 (WNK3/E314Q and WNK3/E314A, and the homologous WNK1/E388A) enhanced the rate of autophosphorylation, and reduced chloride sensitivity. Other WNK3 Cluster mutants reduced the rate of autophosphorylation activity coupled with greater chloride sensitivity than wild-type. The water and chloride regulation thus appear linked. The lower activity of some mutants may reflect effects on catalysis. Crystallography showed that activating mutants introduced conformational changes in similar parts of the structure to those induced by PEG400. WNK activating mutations and crystallography support a role for CWN1 in WNK inhibition consistent with water functioning as an allosteric ligand.

Towards real-world state of health estimation: Part 2, system level method using electric vehicle field data

Accurate battery health estimation is pivotal for ensuring the safety and performance of electric vehicles (EVs). While predominant research has centered on laboratory-level single cells, the accurate estimation of battery system capacity using real-world data remains a challenge, due to the vast diversity in battery types, operating conditions, data recordings, etc. To this end, we release three large-scale field datasets of 464 EVs from three manufacturers, comprising over 1.2 million charging snippets. The EVs’ capacity and State of Health (SOH) are effectively labeled using K-means to cluster and concatenate charging snippets. A robust data-driven framework integrating a Gated Convolutional Neural Network (GCNN) for estimating battery capacity is proposed, and the results outperform other machine learning models. In addition, a fine-tuning technique is employed to further enhance model efficacy on new datasets and with limited training data. This research not only advances battery health estimations but also paves the way for broader applications in battery management systems (BMSs), offering a scalable solution to real-world challenges in battery technology.

A negatively charged cluster in the disordered acidic domain of GPIHBP1 provides selectivity in the interaction with lipoprotein lipase

GPIHBP1 is a membrane protein of endothelial cells that transports lipoprotein lipase (LPL), the key enzyme in plasma triglyceride metabolism, from the interstitial space to its site of action on the capillary lumen. An intrinsically disordered highly negatively charged N-terminal domain of GPIHBP1 contributes to the interaction with LPL. In this work, we investigated whether the plethora of heparin-binding proteins with positively charged regions found in human plasma affect this interaction. We also wanted to know whether the role of the N-terminal domain is purely non-specific and supportive for the interaction between LPL and full-length GPIHBP1, or whether it participates in the specific recognition mechanism. Using surface plasmon resonance, affinity chromatography, and FRET, we were unable to identify any plasma component, besides LPL, that bound the N-terminus with detectable affinity or affected its interaction with LPL. By examining different synthetic peptides, we show that the high affinity of the LPL/N-terminal domain interaction is ensured by at least ten negatively charged residues, among which at least six must sequentially arranged. We conclude that the association of LPL with the N-terminal domain of GPIHBP1 is highly specific and human plasma does not contain components that significantly affect this complex.

Ru3@Mo2CO2 MXene single-cluster catalyst for highly efficient N2-to-NH3 conversion.

Single-cluster catalysts (SCCs) representing structurally well-defined metal clusters anchored on support tend to exhibit tunable catalytic performance for complex redox reactions in heterogeneous catalysis. Here we report a theoretical study on an SCC of Ru3@Mo2CO2 MXene for N2-to-NH3 thermal conversion. Our results show that Ru3@Mo2CO2 can effectively activate N2 and promotes its conversion to NH3 through an association mechanism, in which the rate-determining step of NH2* + H* → NH3* has a low energy barrier of 1.29eV. Notably, with the assistance of Mo2CO2 support, the positively charged Ru3 cluster active site can effectively adsorb and activate N2, leading to 0.74 |e| charge transfer from Ru3@Mo2CO2 to the adsorbed N2. The supported Ru3 also acts as an electron reservoir to regulate the charge transfer for various intermediate steps of ammonia synthesis. Microkinetic analysis shows that the turnover frequency of the N2-to-NH3 conversion on Ru3@Mo2CO2 is as high as 1.45×10-2 s-1 site-1 at a selected thermodynamic condition of 48bar and 700K, the performance of which even surpasses that of the Ru B5 site and Fe3/θ-Al2O3(010) reported before. Our work provides a theoretical understanding of the high stability and catalytic mechanism of Ru3@Mo2CO2 and guidance for further designing and fabricating MXene-based metal SCCs for ammonia synthesis under mild conditions.

Ring Structures of Metal Atom Doped C9, C11, and C13 Clusters from Ab Initio Calculations-The Finding of a Gd@C13 Magnetic Superatom Ring.

Pure C9 clusters have a linear chain structure. However, here, we report using ab initio calculations the transformation of a chain into a cyclic ring structure with the capping of Ca, Sr, and Ba atoms. Further calculations on neutral and charged clusters doped with Sc, Y, and La atoms show stabilization of a cation C9 isoelectronic cyclic ring capped with the metal (M) atom, but anion clusters doped with these trivalent atoms form a C10 like MC9 ring, which deforms to a necklace structure. Both the ring structures correspond to electronic shell closing with 20 delocalized valence electrons in a disk jellium model and have a large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap. Calculations of IR and Raman spectra show no imaginary frequency, suggesting that the structures are stable. Addition of two C atoms to the ring structure of LaC9 leads to a capped ring structure of the cation LaC11 and an open ring structure of the LaC11 anion. Further addition of two C atoms leads to a La@C13 cation as well as Ca@C13 and Sr@C13 neutral wheel-shaped rings with endohedral doping of the M atom. These novel ring structures have a large HOMO-LUMO gap of more than 4 eV and are magic with electronic shell closing corresponding to 28 delocalized valence electrons in a disk jellium model. There is π aromaticity in this ring satisfying 4n+2 (n = 3) Hückel's rule with 14 valence electrons. Interestingly, when the dopant is a Gd atom, there is a formation of a magnetic superatom ring Gd@C13 + with 7 μB magnetic moments due to seven 4f up-spin states of Gd being fully occupied. Bonding in these novel ring structures is discussed.

Cluster Formation of Self-Assembled Triarylbismuthanes and Charge Transport Characterizations of Gold-Triarylbismuthane-Gold Junctions.

Organometallic molecules are promising for molecular electronic devices due to their potential to improve electrical conductance through access to complex orbital covalency that is not available to light-element organic molecules. However, studies of the formation of organometallic monolayers and their charge transport properties are scarce. Here, we report the cluster formation and charge transport properties of gold-triarylbismuthane-gold molecular junctions. We found that triarylbismuthane molecules with -CN anchoring groups form clusters during the creation of self-assembled submonolayers. This clustering is attributed to strong interactions between the bismuth (Bi) center and the nitrogen atom in the -CN group of adjacent molecules. Examination of the influence of -NH2 and -CN anchoring groups on junction conductance revealed that, despite a stronger binding energy between the -NH2 group and gold, the conductance per molecular unit (i.e., molecule for the -NH2 group and cluster for the -CN group) is higher with the -CN anchoring group. Further analysis showed that an increase in the number of -CN groups from one to three within the junctions leads to a decrease in conductance while increasing the size of the cluster. This demonstrates the significant effects of different anchoring groups and the impact of varying the number of -CN groups on both the charge transport and cluster formation. This study highlights the importance of selecting the appropriate anchoring group in the design of molecular junctions. Additionally, controlling the size and formation of clusters can be a strategic approach to engineering charge transport in molecular junctions.

Electrostatic Surface Charging by Water Dewetting.

Water dewetting generates static electricity. We reviewed historical experiments of this phenomenon, and we studied the charging of polymer slides and metal electrode supported polymer films withdrawn vertically from a pool of aqueous solutions. For pure water, charging was negative and surface charge densities increased with the speed of dewetting, which we explain by the thermally activated entrainment of nanometer-sized water droplets or clusters charged by unbalanced adsorbed electric double-layer ions. Surface charge densities increased for reduced polymer film thickness following a power law, which we explain by reduced discharge of the entrained water volumes. At low salinity c ≲ 10 μM, charging was proportional to electrokinetic interfacial charge densities: the negative charging was increased for alkaline solutions and for most salts at μM concentrations and the charge polarity was inversed to positive for a cationic surfactant, a salt with a highly positively charged cation, and for a strong acid at approximately pH 4. Charging was reduced again for c ≳ 100 μM, especially at high dewetting speeds and for chaotropic ions, which we explain by the entrainment of larger and more discharged droplets. We determined adsorption energies of the charged water clusters on the dewetted surface from thermally stimulated discharge of the charged polymer slides and we show that the surface charge distribution, imaged by charged toner powders and measured microscopically by Kelvin probe force microscopy, is a record of the dewetting process that provides spatial and kinetic information about the three-phase contact line motion.

How Does HF-DFT Achieve Chemical Accuracy for Water Clusters?

Bolstered by recent calculations of exact functional-driven errors (FEs) and density-driven errors (DEs) of semilocal density functionals in the water dimer binding energy [Kanungo, B. J. Phys. Chem. Lett. 2024, 15, 323-328], we investigate approximate FEs and DEs in neutral water clusters containing up to 20 monomers, charged water clusters, and alkali- and halide-water clusters. Our proxy for the exact density is r2SCAN 50, a 50% global hybrid of exact exchange with r2SCAN, which may be less correct than r2SCAN for the compact water monomer but importantly more correct for long-range electron transfers in the noncompact water clusters. We show that SCAN makes substantially larger FEs for neutral water clusters than r2SCAN, while both make essentially the same DEs. Unlike the case for barrier heights, these FEs are small in a relative sense and become large in an absolute sense only due to an increase in cluster size. SCAN@HF, short for SCAN evaluated on the Hartree-Fock (HF) density, produces a cancellation of errors that makes it chemically accurate for predicting the absolute binding energies of water clusters. Likewise, adding a long-range dispersion correction to r2SCAN@HF, as in the composite method HF-r2SCAN-DC4, makes its FE more negative than in r2SCAN@HF, permitting a near-perfect cancellation of FE and DE. r2SCAN by itself (and even more so, r2SCAN evaluated on the r2SCAN 50 density), is almost perfect for the energy differences between water hexamers, and thus probably also for liquid water away from the boiling point. Thus, the accuracy of composite methods like SCAN@HF and HF-r2SCAN-DC4 is not due to the HF density being closer to the exact density, but to a compensation of errors from its greater degree of localization. We also give an argument for the approximate reliability of this unconventional error cancellation for diverse molecular properties. Finally, we confirm this unconventional error cancellation for the SCAN description of the water trimer via Kohn-Sham inversion of the CCSD(T) density.

Performance of density-functional-theory and random-phase-approximation methods on the study of transition-metal clusters: the Tan clusters as an example

Recently developed density-functional-theory (DFT) and random-phase-approximation (RPA) methods are used to study competing isomers of some negatively charged Ta clusters, namely Ta12 - and Ta10 -, in an attempt to find a suitable strategy towards accurate studies of transition-metal clusters based on DFT. Also the neutral and cationic forms Ta12 (0,+) of the twelve-atom cluster are studied. The results are compared with experimental information obtained by several methods that differ in the property under study and the total electric charge of the clusters. We find that a careful choice of the density functional, the use of relativistic two-component methods, eventually in combination with all-electron basis sets, and the application of RPA-type methods, may all be necessary steps for a good assessment. Such an assessment should be made in relation to several experimental properties as much as possible.

Inhibition and transport mechanisms of the ABC transporter hMRP5

Human multidrug resistance protein 5 (hMRP5) effluxes anticancer and antivirus drugs, driving multidrug resistance. To uncover the mechanism of hMRP5, we determine six distinct cryo-EM structures, revealing an autoinhibitory N-terminal peptide that must dissociate to permit subsequent substrate recruitment. Guided by these molecular insights, we design an inhibitory peptide that could block substrate entry into the transport pathway. We also identify a regulatory motif, comprising a positively charged cluster and hydrophobic patches, within the first nucleotide-binding domain that modulates hMRP5 localization by engaging with membranes. By integrating our structural, biochemical, computational, and cell biological findings, we propose a model for hMRP5 conformational cycling and localization. Overall, this work provides mechanistic understanding of hMRP5 function, while informing future selective hMRP5 inhibitor development. More broadly, this study advances our understanding of the structural dynamics and inhibition of ABC transporters.

Exciton Dissociation into Charge Carriers in Porphyrinic Metal-Organic Frameworks for Light-Assisted Li-O2 Batteries.

Light-assisted Li-O2 batteries exhibit a high round-trip efficiency attributable to the assistance of light-generated electrons and holes in oxygen reduction and evolution reactions. Nonetheless, the excitonic effect arising from Coulomb interaction between electrons and holes impedes carrier separation, thus hindering efficient utilization of photo-energy. Herein, porphyrinic metal-organic frameworks with (Fe2Ni)O(COO)6 clusters are used as photocathodes to accelerate exciton dissociation into charge carriers for light-assisted Li-O2 batteries. The coupling of Ni 3d and Fe 3d orbitals boosts ligand-to-metal cluster charge transfer, and hence drives exciton dissociation and activates O2 for superoxide (•O2 -) radicals, rather than singlet oxygen (1O2) under photoexcitation. These enable the light-assisted Li-O2 batteries with a low total overvoltage of 0.28V and round-trip efficiency of 92% under light irradiation of 100mW cm-2. This work highlights the excitonic effect in photoelectrochemical processes and provides insights into photocathode design for light-assisted Li-O2 batteries.

Intermediate ions as indicator for local new particle formation

Abstract. Atmospheric aerosol particles have a considerable influence on climate via both aerosol–radiation and aerosol–cloud interactions. A major fraction of global aerosol particles, in terms of their number concentration, is due to atmospheric new particle formation (NPF) that involves both neutral and charged clusters and particles. NPF is the major source of atmospheric intermediate ions, i.e., charged particles with mobility diameters between approx. 2 and 7 nm. We investigate ion concentrations between 1.7 and 3.1 nm at the SMEAR II (Station for Measuring Forest Ecosystem–Atmosphere Relations II) measurement station in Hyytiälä, Finland. Both negative and positive ion number size distributions measured by a Neutral cluster and Air Ion Spectrometer (NAIS) are used. Our aim is to find the best diameter size range of ions for identifying and evaluating the intensity of local intermediate ion formation (LIIF). Intermediate ion formation (IIF) refers to the formation of intermediate ions through NPF, while local means that the growth of such ions from smaller clusters has occurred in close proximity (e.g., within 500 m to 1 km) to the measurement site, i.e., locally. We find that the ions in the mobility diameter size range of 2.0–2.3 nm are the best suited for detection of LIIF. The ion concentrations in this size range indicate the elevated rates of IIF, and the potential distances the growing ions have traveled are smaller than those for larger ions. In addition, in Hyytiälä, the negative ion concentrations are more sensitive to IIF than the positive ion concentrations due to the higher difference in concentrations between periods of IIF and the background. Therefore, we recommend the concentrations of ions with diameters 2.0–2.3 nm as the best choice for identifying and evaluating the intensity of LIIF.

DFTB Simulation of Charged Clusters Using Machine Learning Charge Inference.

We present a modification to self-consistent charge density functional-based tight binding (SCC-DFTB), which allows computation based on approximate atomic charges. We obtain these charges by means of a machine learning (ML) process that combines a Coulomb model with a neural network. This allows us to avoid the SCC cycles in the SCC-DFTB calculation while maintaining its accuracy. The main input of the model is the atomic positions characterized by a set of atom-centered symmetry functions. The charge inference from our ML algorithm is as close as 10-2 units of charge from the exact SCC solution. Our ML-DFTB approach provides a good approximation of the density matrix and of the energy and forces with only a single diagonalization. This is a significant computational saving with respect to the complete SCC algorithm, which allows us to investigate a bigger ensemble of atoms. We show the quality of our approach in the case of charged silicon carbide (SiC) clusters. The ML-DFTB potential energy surface (PES) mimics the SCC-DFTB PES rather well, despite its simplicity. This allows us to obtain the same geometric structure ordering with respect to energy for small clusters. The dissociation barriers for ion emission are well-reproduced, which opens the way to investigating ion field emission and charged cluster stability. The ML-DFTB approach is obviously not limited to charged clusters or SiC materials. It opens a new route to investigate larger clusters than those investigated by standard SCC-DFTB, as well as surface and solid-state chemistry at the atomic level.

Theoretical prediction of low-energy photoelectron spectra of AlnNi- clusters (n = 1-13).

Mixed-metal clusters have long been studied because of their peculiar properties and how they change with cluster size, composition, and charge state and their potential roles in catalysis. The characterization of these clusters is therefore a very important issue. One of the main experimental tools for characterizing their electronic structure is photoelectron spectroscopy. Theoretical computation completes the task by fully determining the structural properties and matching the theoretical predictions to the measured spectra. We present density functional theory computations of the structural, magnetic, and electronic properties of negatively charged mixed AlnNi- clusters with up to 13 Al atoms. The lowest energy structures of the anionic clusters with up to 7 atoms are also found to be low-energy isomers of the neutral counterparts found in the literature. The 13-atom cluster is found to be a quartet and a perfect icosahedron. The predicted photoelectron spectra are also presented and can be used to interpret future experimental data. We also presented indicators that can be used to determine the potential of these systems for single-atom catalysis. These indicators point to smaller clusters to be more reactive as the gap between the Fermi energy and the center of the d-band increases with cluster size and that Ni occupies an internal site for n = 11-13. We speculate that reactivity can be enhanced if one adds an additional Ni atom. The DFT calculations were performed using the Becke exchange and Perdew-Wang/91 correlation functionals (BPW91), a DFT-optimized all-electron basis set for the aluminum atom, and the Stuttgart small core pseudopotential for the Ni atom. All of the computations used the Gaussian 03 software.