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Naphthalene‐Diimide‐Based Ionenes as Universal Interlayers for Efficient Organic Solar Cells

Abstract Self‐doping ionene polymers were efficiently synthesized by reacting functional naphthalene diimide (NDI) with 1,3‐dibromopropane ( NDI‐NI ) or trans ‐1,4‐dibromo‐2‐butene ( NDI‐CI ) via quaternization polymerization. These NDI‐based ionene polymers are universal interlayers with random molecular orientation, boosting the efficiencies of fullerene‐based, non‐fullerene‐based, and ternary organic solar cells (OSCs) over a wide range of interlayer thicknesses, with a maximum efficiency of 16.9 %. NDI‐NI showed a higher interfacial dipole (Δ), conductivity, and electron mobility than NDI‐CI , affording solar cells with higher efficiencies. These polymers proved to efficiently lower the work function ( WF ) of air‐stable metals and optimize the contact between metal electrode and organic semiconductor, highlighting their power to overcome energy barriers of electron injection and extraction processes for efficient organic electronics.

Liu, Ming↗

Experimental and theoretical investigations of rotating algae biofilm reactors (RABRs): Areal productivity, nutrient recovery, and energy efficiency

Microalgae biofilms have been demonstrated to recover nutrients from wastewater and serve as biomass feedstock for bioproducts. However, there is a need to develop a platform to quantitatively describe microalgae biofilm production, which can provide guidance and insights for improving biomass areal productivity and nutrient uptake efficiency. Here, this paper proposes a unified experimental and theoretical framework to investigate algae biofilm growth on a rotating algae biofilm reactor (RABR). Experimental laboratory setups are used to conduct controlled experiments on testing environmental and operational factors for RABRs. We propose a differential–integral equation‐based mathematical model for microalgae biofilm cultivation guided by laboratory experimental findings. The predictive mathematical model development is coordinated with laboratory experiments of biofilm areal productivity associated with ammonia and inorganic phosphorus uptake by RABRs. The unified experimental and theoretical tool is used to investigate the effects of RABR rotating velocity, duty cycle (DC), and light intensity on algae biofilm growth, areal productivity, nutrient uptake efficiency, and energy efficiency in wastewater treatment. Our framework indicates that maintaining a reasonable light intensity range improves biomass areal productivity and nutrient uptake efficiency. Our framework also indicates that faster RABR rotation benefits biomass areal productivity. However, maximizing the nutrient uptake efficiency requires a reasonably low RABR rotating speed. Energy efficiency is strongly correlated with RABR rotating speed and DC.

09 BIOMASS FUELS↗

Electron and photon efficiencies in LHC Run 2 with the ATLAS experiment

Precision measurements of electron reconstruction, identification, and isolation efficiencies and photon identification efficiencies are presented. They use the full Run 2 data sample collected by the ATLAS experiment in pp collisions at a centre-of-mass energy of 13 TeV during the years 2015–2018, corresponding to an integrated luminosity of 139 fb -1 . The measured electron identification efficiencies have uncertainties that are around 30%–50% smaller than the previous Run 2 results due to an improved methodology and the inclusion of more data. A better pile-up subtraction method leads to electron isolation efficiencies that are more independent of the amount of pile-up activity. Updated photon identification efficiencies are also presented, using the full Run 2 data. When compared to the previous measurement, a 30%–40% smaller uncertainty is observed on the photon identification efficiencies, thanks to the increased amount of available data.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

High-Temperature High-Efficiency Solar Thermoelectric Generators

Inspired by recent high-efficiency thermoelectric modules, we consider thermoelectrics for terrestrial applications in concentrated solar thermoelectric generators (STEGs). The STEG is modeled as two subsystems: a TEG, and a solar absorber that efficiently captures the concentrated sunlight and limits radiative losses from the system. The TEG subsystem is modeled using thermoelectric compatibility theory; this model does not constrain the material properties to be constant with temperature. Considering a three-stage TEG based on current record modules, this model suggests that 18% efficiency could be experimentally expected with a temperature gradient of 1000A degrees C to 100A degrees C. Achieving 15% overall STEG efficiency thus requires an absorber efficiency above 85%, and we consider two methods to achieve this: solar-selective absorbers and thermally insulating cavities. When the TEG and absorber subsystem models are combined, we expect that the STEG modeled here could achieve 15% efficiency with optical concentration between 250 and 300 suns.

NESDPS Office of Nuclear Energy Space and Defense ↗

Efficient photocatalytic H2 production via rational design of synergistic spatially-separated dual cocatalysts modified Mn0.5Cd0.5S photocatalyst under visible light irradiation

Noble metal-free highly efficient cocatalysts are very important for cost efficient hydrogen fuel production. While most studies concentrate on single cocatalyst photocatalytic systems. Here, we report on the synthesis of Mn0.5Cd0.5S photocatalyst hetero-architecture with synergistic spatially separated dual cocatalysts Cu2-xS and MoS2 for highly efficient photocatalytic H-2 production. Through tactfully utilizing Cu2-xS/Mn0.5Cd0.5S nanoscale p-n junction to promote efficient transfer of photo-generated holes to Cu2-xS and MoS2 can be located exactly on the different positions where the photo-generated electrons must go through by photo-reduction of (NH4)(2)MoS4. Cu2-xS can be an oxidation active site to assemble photo-generated holes and MoS2 can capture and transport the photon-generated electrons. Therefore the photo-induced carriers can be efficiently separated and transferred to take part in photocatalytic reactions. The prepared Cu2-xS (0.015)/Mn0.5Cd0.5S/MoS2 (3 wt %) photocatalyst shows the highest H-2 production rate of 687.62 mu mol/h, which exceeds the rate of Mn0.5Cd0.5S and Mn0.5Cd0.5S loaded with Cu2-xS or MoS2 alone by 22, 1.7 and 3.48 times, respectively. This work provides a new thought to design efficient spatially separated and synergistic dual cocatalysts modified photocatalysts for H-2 production.

Dual cocatalysts↗

Back-gated graphene anode for more efficient thermionic energy converters

Thermionic energy converters (TECs) are a direct heat-to-electricity conversion technology with great potential for high efficiency and scalability. However, space charge barrier in the inter-electrode gap and high anode work function are major obstacles toward realizing high efficiency. Here, we demonstrate for the first time a prototype TEC using a back-gated graphene anode, a barium dispenser cathode, and a controllable inter-electrode gap as small as 17 µm, which simultaneously addresses these two obstacles. This leads to an electronic conversion efficiency of 9.8% at cathode temperature of 1000 °C, the highest reported by far. We first demonstrate that electrostatic gating of graphene by a 20 nm HfO 2 dielectric layer changes the graphene anode work function by 0.63 eV, as observed from the current-voltage characteristics of the TEC. Next, we show that the efficiency increases by a factor of 30.6 by reducing the gap from 1 mm down to 17 µm, after a mono-layer of Ba is deposited on graphene by the dispenser cathode. Lastlu, we show that electrostatic gating of graphene further reduces the graphene work function from 1.85 to 1.69 eV, leading to an additional 67% enhancement in TEC efficiency. Note that the overall efficiency using the back-gated graphene anode is 6.7 times higher compared with that of a TEC with a tungsten anode and the same inter-electrode gap.

30 DIRECT ENERGY CONVERSION↗

Efficient and mechanically-robust organic solar cells based on vertical stratification modulation through sequential blade-coating

Mechanically durable organic solar cells (OSCs) with high efficiency are deemed as the ideal candidate for the power source of the next generation wearable electronic devices. However, the brittle nature of small molecules in most high-efficiency OSCs consisting of polymer and small molecule encourages easy formation of cracks in the photoactive film under deformation. Here, the vertical composition distribution of the active layer has been well optimized through sequential blade coating to realize highly deformable while efficient OSC. The optimized morphology exhibits distinct donor-rich and homogenous region distributed along the vertical direction in the bulk. The donor-rich region provides sufficient chain entanglements and strong interfaces beneficial for mechanical robustness of film, while homogeneously mixed region offers continuous interpenetrating network to maintain high device through-put, resulting in superior efficiency of 14.4% with high crack-onset strain (COS) of 30.5%. This efficiency versus COS combination is much higher than the best combination reported in all polymer systems (COS of 15.9% and efficiency of 11.1%). To the best of our knowledge, it is the highest COS value achieved in polymer-small molecule systems. As a result, the rational control over vertical stratification demonstrated here would guide researchers in the development of innovative wearable electronics.

36 MATERIALS SCIENCE↗

Developing a new ethylene glycol/H 2 O pretreatment system to achieve efficient enzymatic hydrolysis of sugarcane bagasse cellulose and recover highly active lignin: Countercurrent extraction

Improving pretreatment efficiency is a critical premise in achieving efficient biomass conversion, and obtaining high-performance natural polymers is the guarantee of high-value conversion of biomass. Here, in this study, a new pilot-scale continuous countercurrent pretreatment reaction unit about ethylene glycol-alkali solution was designed for pretreating sugarcane bagasse in order to achieve efficient separation of the three major components of lignocellulose when expanding the scale of pretreatment, reduce lignin deposition on the fiber surface, and obtain highly active lignin and excellent enzymatic hydrolysis efficiency of cellulose. X-ray diffractometer (XRD), X-ray photoelectron spectrometer (XPS), brunauer-emmett-teller (BET) and scanning electron microscope (SEM) methods are used to analyze the structural properties of sugarcane bagasse before and after pretreatment, and high-performance liquid chromatography (HPLC) is used to analyze the monosaccharide components in the enzymatic solution. In addition, the structural properties of the recovered lignin are analyzed by gel permeation chromatography (GPC), 31 P NMR and 2D-HSQC-NMR methods. The results indicate that the system can gain a high cellulose recovery of 92.99% along with a lignin removal of 95.33%, and recovered lignin has low lignin carbohydrate complexes, low condensation, and rich in phenolic hydroxyl groups for 1.95 mmol/g. Meanwhile, the countercurrent pretreatment system can effectively reduce the deposition of lignin on the cellulose surface, which is evidently superior to the non-countercurrent pretreatment and facilitates the efficiency of enzymatic saccharification of substrate, achieving a high glucose yield of 99% as well as a total sugar yield of 91.11%. The method efficiently separates biomass in a green manner, and solid residues are easily hydrolyzed, showing potential for industrial-scale production.

09 BIOMASS FUELS↗

Predicting the oral uptake efficiency of chemicals in mammals: Combining the hydrophilic and lipophilic range

Environmental risk assessment requires models for estimating the bioaccumulation of untested compounds. So far, bioaccumulation models have focused on lipophilic compounds, and only a few have included hydrophilic compounds. Our aim was to extend an existing bioaccumulation model to estimate the oral uptake efficiency of pollutants in mammals for compounds over a wide K{sub ow} range with an emphasis on hydrophilic compounds, i.e. compounds in the lower K{sub ow} range. Usually, most models use octanol as a single surrogate for the membrane and thus neglect the bilayer structure of the membrane. However, compounds with polar groups can have different affinities for the different membrane regions. Therefore, an existing bioaccumulation model was extended by dividing the diffusion resistance through the membrane into an outer and inner membrane resistance, where the solvents octanol and heptane were used as surrogates for these membrane regions, respectively. The model was calibrated with uptake efficiencies of environmental pollutants measured in different mammals during feeding studies combined with human oral uptake efficiencies of pharmaceuticals. The new model estimated the uptake efficiency of neutral (RMSE = 14.6) and dissociating (RMSE = 19.5) compounds with logK{sub ow} ranging from − 10 to + 8. The inclusion of the K{sub hw} improved uptake estimation for 33% of the hydrophilic compounds (logK{sub ow} < 0) (r{sup 2} = 0.51, RMSE = 22.8) compared with the model based on K{sub ow} only (r{sup 2} = 0.05, RMSE = 34.9), while hydrophobic compounds (logK{sub ow} > 0) were estimated equally by both model versions with RMSE = 15.2 (K{sub ow} and K{sub hw}) and RMSE = 15.7 (K{sub ow} only). The model can be used to estimate the oral uptake efficiency for both hydrophilic and hydrophobic compounds. -- Highlights: ► A mechanistic model was developed to estimate oral uptake efficiency. ► Model covers wide logK{sub ow} range (- 10 to + 8) and several mammalian species. ► K{sub ow} and the heptane water partition coefficient K{sub hw} were combined. ► K{sub ow} and K{sub hw} reflect the inner and the outer membrane diffusion resistance. ► Combining K{sub ow} and K{sub hw} improved uptake estimation for hydrophilic compounds.

60 APPLIED LIFE SCIENCES↗

Determinants for Efficient Editing with Cas9-Mediated Recombineering in Escherichia coli

In E. coli, editing efficiency with Cas9-mediated recombineering varies across targets due to differences in the level of Cas9:gRNA-mediated DNA double-strand break (DSB)-induced cell death. We found that editing efficiency with the same gRNA and repair template can also change with target position, cas9 promoter strength, and growth conditions. Incomplete editing, off-target activity, nontargeted mutations, and failure to cleave target DNA even if Cas9 is bound also compromise editing efficiency. These effects on editing efficiency were gRNA-specific. We propose that differences in the efficiency of Cas9:gRNA-mediated DNA DSBs, as well as possible differences in binding of Cas9:gRNA complexes to their target sites, account for the observed variations in editing efficiency between gRNAs. We show that editing behavior using the same gRNA can be modified by mutating the gRNA spacer, which changes the DNA DSB activity. Finally, we discuss how variable editing with different gRNAs could limit high-throughput applications and provide strategies to overcome these limitations.

59 BASIC BIOLOGICAL SCIENCES↗

Comparison of Energy Efficiency and Power Density in Pressure Retarded Osmosis and Reverse Electrodialysis

Pressure retarded osmosis (PRO) and reverse electrodialysis (RED) are emerging membrane-based technologies that can convert chemical energy in salinity gradients to useful work. The two processes have intrinsically different working principles: controlled mixing in PRO is achieved by water permeation across salt-rejecting membranes, whereas RED is driven by ion flux across charged membranes. This study compares the energy efficiency and power density performance of PRO and RED with simulated technologically available membranes for natural, anthropogenic, and engineered salinity gradients (seawater-river water, desalination brine-wastewater, and synthetic hypersaline solutions, respectively). The analysis shows that PRO can achieve both greater efficiencies (54-56%) and higher power densities (2.4-38 W/m(2)) than RED (18-38% and 0.77-1.2 W/m(2)). The superior efficiency is attributed to the ability of PRO membranes to more effectively utilize the salinity difference to drive water permeation and better suppress the detrimental leakage of salts. On the other hand, the low conductivity of currently available ion exchange membranes impedes RED ion flux and, thus, constrains the power density. Both technologies exhibit a trade-off between efficiency and power density: employing more permeable but less selective membranes can enhance the power density, but undesired entropy production due to uncontrolled mixing increases and some efficiency is sacrificed. When the concentration difference is increased (i.e., natural -> anthropogenic -> engineered salinity gradients), PRO osmotic pressure difference rises proportionally but not so for RED Nernst potential, which has logarithmic dependence on the solution concentration. Because of this inherently different characteristic, RED is unable to take advantage of larger salinity gradients, whereas PRO power density is considerably enhanced. Additionally, high solution concentrations suppress the Donnan exclusion effect of the charged RED membranes, severely reducing the permselectivity and diminishing the energy conversion efficiency. This study indicates that PRO is more suitable to extract energy from a range of salinity gradients, while significant advancements in ion exchange membranes are likely necessary for RED to be competitive with PRO.

Yip, NY↗

Multiple mechanisms drive phage infection efficiency in nearly identical hosts

Phage-host interactions are critical to ecology, evolution, and biotechnology. Central to those is infection efficiency, which remains poorly understood, particularly in nature. Here we apply genome-wide transcriptomics and proteomics to investigate infection efficiency in nature’s own experiment: two nearly-identical (genetically and physiologically) Bacteroidetes bacterial strains (host18 and host38) that are genetically intractable, but environmentally important, where phage infection efficiency varies. On host18, specialist phage phi18:3 infects efficiently whereas generalist phi38:1 infects inefficiently. On host38, only phi38:1 infects, and efficiently. Overall, phi18:3 globally repressed host18’s transcriptome and proteome, expressed genes that likely evaded host restriction/modification (R/M) defenses and controlled its metabolism, and synchronized phage transcription with translation. In contrast, phi38:1 failed to repress host18’s transcriptome and proteome, did not evade host R/M defenses or express genes for metabolism control, did not synchronize transcripts with proteins and its protein abundances were likely targeted by host proteases. However, on host38, phi38:1 globally repressed host transcriptome and proteome, synchronized phage transcription with translation, and infected host38 efficiently. Together these findings reveal multiple infection inefficiencies. While this contrasts the single mechanisms often revealed in laboratory mutant studies, it likely better reflects the phage-host interaction dynamics that occur in nature.

59 BASIC BIOLOGICAL SCIENCES↗

Supported black phosphorus nanosheets as hydrogen-evolving photocatalyst achieving 5.4% energy conversion efficiency at 353 K

Solar-driven water splitting using powdered catalysts is considered as the most economical means for hydrogen generation. However, four-electron-driven oxidation half-reaction showing slow kinetics, accompanying with insufficient light absorption and rapid carrier combination in photocatalysts leads to low solar-to-hydrogen energy conversion efficiency. Here, we report amorphous cobalt phosphide (Co-P)-supported black phosphorus nanosheets employed as photocatalysts can simultaneously address these issues. The nanosheets exhibit robust hydrogen evolution from pure water (pH = 6.8) without bias and hole scavengers, achieving an apparent quantum efficiency of 42.55% at 430 nm and energy conversion efficiency of over 5.4% at 353 K. This photocatalytic activity is attributed to extremely efficient utilization of solar energy (~75% of solar energy) by black phosphorus nanosheets and high-carrier separation efficiency by amorphous Co-P. The hybrid material design realizes efficient solar-to-chemical energy conversion in suspension, demonstrating the potential of black phosphorus-based materials as catalysts for solar hydrogen production.

14 SOLAR ENERGY↗

Integrating theory, synthesis, spectroscopy and device efficiency to design and characterize donor materials for organic photovoltaics: a case study including 12 donors

There have been remarkable improvements in the power conversion efficiency of solution-processable Organic Photovoltaics (OPV) have largely been driven by the development of novel narrow bandgap copolymer donors comprising an electron-donating (D) and an electron-withdrawing (A) group within the repeat unit. The large pool of potential D and A units and the laborious processes of chemical synthesis and device optimization, has made progress on new high efficiency materials slow with a few new efficient copolymers reported every year despite the large number of groups pursuing these materials. In our paper we present an integrated approach toward new narrow bandgap copolymers that uses theory to guide the selection of materials to be synthesized based on their predicted energy levels, and time-resolved microwave conductivity (TRMC) to select the best-performing copolymer–fullerene bulk heterojunction to be incorporated into complete OPV devices. We validate our methodology by using a diverse group of 12 copolymers, including new and literature materials, to demonstrate good correlation between (a) theoretically determined energy levels of polymers and experimentally determined ionization energies and electron affinities and (b) photoconductance, measured by TRMC, and OPV device performance. The materials used here also allow us to explore whether further copolymer design rules need to be incorporated into our methodology for materials selection. For example, we explore the effect of the enthalpy change (ΔH) during exciton dissociation on the efficiency of free charge carrier generation and device efficiency and find that ΔH of -0.4 eV is sufficient for efficient charge generation.

14 SOLAR ENERGY↗

Efficient solar-driven electrochemical CO 2 reduction to hydrocarbons and oxygenates

Solar to chemical energy conversion could provide an alternative to mankind's unsustainable use of fossil fuels. One promising approach is the electrochemical reduction of CO 2 into chemical products, in particular hydrocarbons and oxygenates which are formed by multi-electron transfer reactions. Here, a nanostructured Cu-Ag bimetallic cathode is utilized to selectively and efficiently facilitate these reactions. When operated in an electrolysis cell, the cathode provides a constant energetic efficiency for hydrocarbon and oxygenate production. As a result, when coupled to Si photovoltaic cells, solar conversion efficiencies of 3-4% to the target products are achieved for 0.35 to 1 Sun illumination. Use of a four-terminal III-V/Si tandem solar cell configuration yields a conversion efficiency to hydrocarbons and oxygenates exceeding 5% at 1 Sun illumination. Here, this study provides a clear framework for the future advancement of efficient solar-driven CO 2 reduction devices. In a process analogous to natural photosynthesis, solar-driven reduction of carbon dioxide to hydrocarbon and oxygenate products is demonstrated with an overall efficiency exceeding 5%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Morphology control enables thickness-insensitive efficient nonfullerene polymer solar cells

Owing to the use of cost-effective materials and excellent stability, nonfullerene polymer solar cells (PSCs) have great potential for realizing large-area industrial production. In contrast to fullerene-based devices, non-fullerene PSCs have exhibited a superior photovoltaic performance with up to 12% efficiency and long-term thermal stability. Presently, one of the major factors hindering industrial production is the high sensitivity of the power conversion efficiency (PCE) to thickness variations, which can significantly affect the manufacturing yields and production costs of roll-to-roll processing. Specifically, the device fill factors and PCEs of many high-efficiency nonfullerene PSCs show a significant loss when the thickness of the active layer is over 100 nm. In order to achieve high output capabilities earlier, there is an urgent need to find a processing method to fabricate high-efficiency thick-film nonfullerene PSCs. Controlling the morphology and performance sensitivity in thick-film non-fullerene devices is a great challenge in the field. In this paper, we present a simple morphology optimization method via thermal annealing to fabricate highly efficient thickness-insensitive non-fullerene PSCs. After this treatment, PBDB-T/IT-M-based nonfullerene PSCs can afford an impressive PCE of up to ~9.4% at an active layer thickness of 250 nm. In addition, the devices with an active layer thickness of 400 nm still maintain a high efficiency close to 9%. The photovoltaic properties and morphology parameters resolved from hard and soft X-ray scattering clearly indicate that thermal annealing plays a key role in improving the film thickness insensitivity for non-fullerene PSCs.

14 SOLAR ENERGY↗

Evidence of trap-assisted Auger recombination in low radiative efficiency MBE-grown III-nitride LEDs

By studying low radiative efficiency blue III-nitride light emitting diodes (LEDs), we find that the ABC model of recombination commonly used for understanding efficiency behavior in LEDs is insufficient and that additional effects should be taken into account. We propose a modification to the standard recombination model by incorporating a bimolecular nonradiative term. The modified model is shown to be in much better agreement with the radiative efficiency data and to be more consistent than the conventional model with very short carrier lifetimes measured by time-resolved photoluminescence in similar, low radiative efficiency material. Here, we present experimental evidence that a hot carrier-generating process is occurring within these devices, in the form of measurements of forward photocurrent under forward bias. The forward photocurrent, due to hot carrier generation in the active region, is present despite the lack of any "efficiency droop"-the usual signature of band-to-band Auger recombination in high-quality III-nitride LEDs. Hot carrier generation in the absence of band-to-band Auger recombination implies that some other source of hot carriers exists within these low radiative efficiency devices, such as trap-assisted Auger recombination.

36 MATERIALS SCIENCE↗

Determining the bubble nucleation efficiency of low-energy nuclear recoils in superheated C 3 F 8 dark matter detectors

The bubble nucleation efficiency of low-energy nuclear recoils in superheated liquids plays a crucial role in interpreting results from direct searches for weakly interacting massive particle (WIMP) dark matter. Here, the PICO collaboration presents the results of the efficiencies for bubble nucleation from carbon and fluorine recoils in superheated C 3 F 8 from calibration data taken with five distinct neutron spectra at various thermodynamic thresholds ranging from 2.1 to 3.9 keV. Instead of assuming any particular functional forms for the nuclear recoil efficiency, a generalized piecewise linear model is proposed with systematic errors included as nuisance parameters to minimize model-introduced uncertainties. A Markov chain Monte Carlo routine is applied to sample the nuclear recoil efficiency for fluorine and carbon at 2.45 and 3.29 keV thermodynamic thresholds simultaneously. The nucleation efficiency for fluorine was found to be ≥ 50% for nuclear recoils of 3.3 keV (3.7 keV) at a thermodynamic Seitz threshold of 2.45 keV (3.29 keV), and for carbon the efficiency was found to be ≥ 50% for recoils of 10.6 keV (11.1 keV) at a threshold of 2.45 keV (3.29 keV). Simulated datasets are used to calculate a p value for the fit, confirming that the model used is compatible with the data. The fit paradigm is also assessed for potential systematic biases, which although small, are corrected for. Additional steps are performed to calculate the expected interaction rates of WIMPs in the PICO-60 detector, a requirement for calculating WIMP exclusion limits.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗