Lowest Unoccupied Molecular Orbital Energy Research Articles

Zerovalent Iron/Cu Combined Degradation of Halogenated Disinfection Byproducts and Quantitative Structure-Activity Relationship Modeling.

Previous studies have reported that zerovalent iron (ZVI) can reduce several aliphatic groups of disinfection byproducts (DBPs) (e.g., haloacetic acids and haloacetamides) effectively, and the removal efficiency can be significantly improved by metallic copper. Information regarding ZVI/Cu combined degradation of different types of halogenated DBPs can help understand the fate of overall DBPs in drinking water distribution and storage systems consisting of unlined cast iron/copper pipes and related potential control strategies. In this study, we found that, besides aliphatic DBPs, many groups of new emerging aromatic DBPs formed in chlorinated and chloraminated drinking water can be effectively degraded by ZVI/Cu; meanwhile, total organic halogen and total ion intensity were reduced significantly after treatment. Moreover, a robust quantitative structure-activity relationship model was developed and validated based on the ZVI/Cu combined degradation rate constants of 14 typical aromatic DBPs; it can predict the degradation rate constants of other aromatic DBPs for screening and comparative purposes, and the optimized descriptors indicate that DBPs possessing a lower value of the lowest unoccupied molecular orbital energy and a higher value of dipole moment tend to present higher degradation rate constants. In addition, toxicity data of 47 DBPs (belonging to 18 groups) were predicted by two previously established toxicity models, demonstrating that, although most DBPs exhibit higher toxicity than their dehalogenated products, some DBPs show lower toxicity than their lowly halogenated analogs.

Revisiting Hole Injection in Quantum Dot Light‐Emitting Diodes

AbstractInjecting holes from the hole transport layer (HTL) into the quantum dot (QD) emitting layer in quantum dot light‐emitting diodes (QLEDs) is considered challenging due to the presence of a relatively high hole injection barrier at the HTL/QD interface. However, QLEDs with exceptional brightness and efficiency are achieved, prompting a reevaluation of the traditional hole injection mechanisms. This study examines the hole injection mechanism in QLEDs using a combination of experiments and simulations. The results demonstrate that the applied bias significantly reduces the barrier height between the highest occupied molecular orbital level of the HTL and the valence band (VB) of the QDs, facilitating hole injection. The bending of the lowest unoccupied molecular orbital energy level of the HTL at the HTL/QD interface confines electrons within the QD, effectively minimizing leakage current. Additionally, the triangle‐shaped potential barrier arising from the bending of the VB energy level of the QDs creates favorable conditions for hole–tunneling injection. Moreover, both simulations and experiments consistently demonstrate that the predominant pathway for hole injection from the HTL to the QDs in the QLED device involved thermally assisted tunneling. This study is important to understand the hole injection mechanism in QLEDs.

The tribo-piezoelectric microscopic coupling mechanism of ferroelectric polymers and the synchronous online monitoring of load distribution/roller speed for intelligent bearings

The tribo-piezoelectric microscopic coupling mechanism of ferroelectric polymers remains elusive due to the complicated interfacial electron transfer behavior and dipole-dipole interactions, limiting the development of high-performance tribo-piezoelectric hybrid nanogenerators. Herein, we take PVDF-Cu as an example to investigate the tribo-piezoelectric coupling mechanism at the ferroelectric polymer/metal interface under compression via first-principles calculations and KPFM experiments. It is revealed that the local deformation of the ferroelectric β-phase PVDF molecular chain not only concentrates the LUMO (lowest unoccupied molecular orbital) in the deformed region and lowers the LUMO energy level, but also changes the orientation and polarity of the dipoles, thus enhancing the triboelectric and piezoelectric charges. Furthermore, this work identifies dipole-dipole interactions and intramolecular/intermolecular electron transfer as the key intrinsic factors that promote the synergistic enhancement of triboelectricity and piezoelectricity. Specifically, the intramolecular and intermolecular electron transfer within the β-phase PVDF induced by the interfacial electron transfer enhances the dipole polarization, thus enhancing the piezoelectric effect, which in turn generates stronger dipole-dipole interactions to provide additional electrostatic potential energy for electrons in the polymer, finally enhancing the interfacial triboelectric effect again. On this basis, we propose the microscopic coupled electrification model at the ferroelectric polymer/metal interface and clarify that the triboelectric and piezoelectric effects dominate at low and high pressures, respectively. Inspired by the above microscopic mechanism, we regulate the ferroelectric β phase of PVDF film to develop a tribo-piezoelectric coupled pressure sensor(T-PPS) with high sensitivity(0.95 V/kPa) and wide measurement range(>10 MPa). In addition, benefiting from the excellent sensing characteristics of T-PPS, we propose a novel strategy based on pressure fluctuation detection of the bearing outer ring, enabling the high-precision synchronous online testing of load distribution and roller speed for intelligent bearings. This method can address the problems of existing measurements such as the destruction of bearings structure, interference with cage motion, and low integration.

An In-Situ Cyanidation Strategy to Access Tetracyanodiacenaphthoanthracene Diimides with High Electron Mobilities Exceeding 10 cm2 V-1 s-1.

A family of novel highly π-extended tetracyano-substituted acene diimides, named as tetracyanodiacenaphthoanthracene diimides (TCDADIs), are synthesized using a facile four-fold Knoevenagel condensation strategy. Unlike conventional cyano substitution reactions, our approach enables access to a large π-conjugated backbone with the in-situ formation of four cyano substitutes at room temperature while avoiding extra cyano-functionalization reactions. TCDADIs decorated with different N-alkyl substituents present good solubility, near-coplanar backbones, good crystallinity, and low-lying lowest unoccupied molecular orbital energies of -4.33 eV, all of which contribute to desirable electron-transport performance when applied to organic field-effect transistors (OFET). The highest electron mobility of OFET based on 2-hexyldecyl-substituted TCDADIs single crystal reaches 12.6 cm2 V-1 s-1, which is not only among the highest values for the reported n-type organic semiconductor materials (OSMs) but also exceeds that of most n-type OSMs decorated with imide units.

An In‐Situ Cyanidation Strategy To Access Tetracyanodiacenaphthoanthracene Diimides with High Electron Mobilities Exceeding 10 cm2 V−1 s−1

AbstractA family of novel highly π‐extended tetracyano‐substituted acene diimides, named as tetracyanodiacenaphthoanthracene diimides (TCDADIs), have been synthesized using a facile four‐fold Knoevenagel condensation strategy. Unlike conventional cyano substitution reactions, our approach enables access to a large π‐conjugated backbone with the in‐situ formation of four cyano substitutents at room temperature while avoiding extra cyano‐functionalization reactions. TCDADIs decorated with different N‐alkyl substituents present good solubility, near‐coplanar backbones, good crystallinity, and low‐lying lowest unoccupied molecular orbital energies of −4.33 eV, all of which contribute to desirable electron‐transport performance when applied in organic field‐effect transistors (OFET). The highest electron mobility of an OFET based on a 2‐hexyldecyl‐substituted TCDADI single crystal reaches 12.6 cm2 V−1 s−1, which is not only among the highest values for the reported n‐type organic semiconductor materials (OSMs) but also exceeds that of most n‐type OSMs decorated with imide units.

The Role of Energy Offsets on Charge Photogeneration Dynamics in Y‐Series Molecules‐Based Polymer Solar Cells

Recent research has revealed that low‐energy offset polymer solar cells (PSCs) are capable of a power conversion efficiency of over 19%. However, it is unclear how energy offsets and the charge photogeneration process are correlated. Herein, the effect of energy offsets on charge photogeneration dynamics for Y‐series molecules (Y5, Y6, Y10, and BTP‐4F‐12)‐based PSCs with the variations of the lowest unoccupied molecular orbital energy offsets (ΔELUMO) of 0.11–0.42 eV and the highest occupied molecular orbital energy offsets (ΔEHOMO) of 0.08–0.23 eV utilizing steady‐state and time‐resolved spectroscopies is studied. The steady‐state measurement shows that the probability of photoluminescence quenching via energy transfer for the donor exciton reduces with the increasing ΔELUMO. It is found that even in PM6:Y6 with the highest ΔELUMO, ≈18% of PM6 exciton dissociated via the path of “energy transfer first and then hole transfer,” manifesting the energy transfer also plays a vital role in the process of exciton dissociation. Furthermore, it is found that the PM6 exciton can efficiently dissociate under the ΔELUMO of 0.11 eV. After photoexcitation of the Y‐series molecule acceptors, the exciton dissociation efficiency enhances with the increase of ΔEHOMO. Besides, the higher energy offsets, the lower charge recombination rate in the ultrafast timescale has been found from the transient absorption measurement. These findings reveal that energy offsets are important for charge photogeneration and recombination in an ultrafast timescale for Y‐series molecule‐based PSCs, which may shed light on the design of high‐performance PSCs.

Indolocarbazole-Based Photo-Crosslinkable Hole-Transporting Layer for Efficient Solution-Processed Organic Light-Emitting Diodes.

We designed and synthesized a new indolocarbazole-based polymer, poly(N,N-diphenyl(5,11-dihexylindolo[3,2,1-jk]carbazol-2-yl)amine) (PICA), for solution-processed organic light-emitting diodes (OLEDs). The highest occupied and lowest unoccupied molecular orbital energy levels of this polymer, -5.25 and -2.46 eV, respectively, are suitable for hole transport from the anode to the emissive layer. PICA was photo-crosslinked by UV irradiation with ethane-1,2-diyl bis(4-azido-2,3,5,6-tetrafluorobenzoate) (FPA) as the photoinitiator. Successful crosslinking was confirmed by a decreased intensity in the azide-stretching FT-IR peak and solvent test with toluene (a suitable solvent for PICA). The PICA film photo-crosslinked with 3 wt% FPA showed enhanced solvent resistance (90%) compared to the non-crosslinked neat PICA film (<20%). Moreover, OLED devices using PICA-based hole-transporting layers exhibited better device performance (EQE/LE/PE: 8.88%/12.97/8.12 in red devices, 10.84%/38.47 cd/A/25.06 lm/W in green devices) than those using poly-TPD:FPA. We demonstrated that the photo-crosslinked PICA can be applied as a hole-transporting layer in solution-processed OLEDs.

Regulating energy gap in Ir-based ionic complexes to generate near-infrared emissions: Application in solid-state light-emitting electrochemical cells

Solid-state light-emitting electrochemical cells (LECs) exhibit high potential for commercial electronics owing to their simple solution-processable device architectures, low-voltage operation, and compatibility with inert metal electrodes. However, the low device efficiency of most deep-red and near-infrared (NIR) LECs hinders their application (external quantum efficiency (EQE) < 1.00%). In this study, we demonstrate a simple method to tune the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of iridium-based ionic transition metal complexes (iTMCs) to generate NIR emissions. We investigate a series of cationic iridium complexes with small energy gaps, with 2,2′-bibenzo[d]thiazole fixed as N^N ligand moiety mainly controlling the LUMO energy level, changing a series of C^N ligands. All complexes exhibited deep red/NIR phosphorescence, and these combined devices provided emission peaks at 690–730 nm and were applied as components in LECs, exhibiting a maximum EQE of 1.78% in electroluminescence devices. Using a host–guest emission system with the iridium complex YIr as the host and complex TBBI as the guest, the highest EQE of LECs could be further enhanced to>2.34%, which is the highest value reported for NIR LECs.

Development of novel acceptors with deep LUMO energy levels

Pure-organic red exciplex emitters are far from satisfactory in terms of quantity and efficiency. The narrow lowest unoccupied molecular orbital (LUMO) energy levels range of reported acceptors together with the intrinsic exciton non-radiative decay are the dominant factors restricting the progress of red exciplexes. Herein, two acceptor molecules operating at unique LUMO of -3.51 and -3.56 eV, namely 4-(6-([1, 1’: 3’, 1”-terphenyl]-5’-yl)-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl) benzonitrile (CNAI-tPh) and 4-(6-(4-(4, 6-diphenyl-1, 3, 5-triazin-2-yl)phenyl)-1, 3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl) benzonitrile (CNAI-TRz), were developed. Through binding to a donor whose HOMO energy level is -5.53 eV, the CNAI-TRz-related OLEDs attained a higher device efficiency amounting to 7.7% with a red-shifted spectrum compared to the CNAI-tPh-related devices. These results are remarkable among the reported pure-organic red exciplex-based OLEDs and demonstrate the tremendous potential of our synthesized acceptors in efficient red exciplexes.

Unveiling controlling factors of the S0/S1 minimum-energy conical intersection (3): Frozen orbital analysis based on the spin-flip theory.

Conical intersections (CIs), which indicate the crossing of two or more adiabatic electronic states, are crucial in the mechanisms of photophysical, photochemical, and photobiological processes. Although various geometries and energy levels have been reported using quantum chemical calculations, the systematic interpretation of the minimum energy CI (MECI) geometries is unclear. A previous study [Nakai et al., J. Phys. Chem. A 122, 8905 (2018)] performed frozen orbital analysis (FZOA) based on time-dependent density functional theory (TDDFT) at the MECI formed between the ground and first electronic excited states (S0/S1 MECI), thereby inductively clarifying two controlling factors. However, one of the factors that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy gap became close to the HOMO-LUMO Coulomb integral was not valid in the case of spin-flip TDDFT (SF-TDDFT), which is frequently used as a means of the geometry optimization of MECI [Inamori et al., J. Chem. Phys. 152, 144108 (2020)]. This study revisited the controlling factors using FZOA for the SF-TDDFT method. Based on spin-adopted configurations within a minimum active space, the S0-S1 excitation energy is approximately represented by the HOMO and LUMO energy gap ΔεHL, a contribution from Coulomb integrals JHL″ and that from the HOMO-LUMO exchange integral KHL″. Furthermore, numerical applications of the revised formula at the SF-TDDFT method confirmed the control factors of S0/S1 MECI.

Development of QSPR models for furan derivatives as corrosion inhibitors for mild steel

The quantitative structure-property relationship QSPR method has been used to analyze the corrosion inhibition properties of furan derivative inhibitors against mild steel. This modeling is based on the correlation between corrosion inhibition efficiency (IE%) and several electronic properties of compounds such as EHOMO (highest occupied molecular orbital energy), ELUMO (lowest unoccupied molecular orbital energy), EL-H (gap energy), μ (dipole moment), IP (ionization potential), EA (electron affinity), ƞ (hardness), σ (softness), χ (electronegativity), ∆N (fraction of electron transfer), ω (electrophilicity index), ∆EB-D (back-donation energy), Log P, Vm (critical volume), and Mr (relative molecular mass). These properties were calculated using DFT at B3LYP/6–31 G(d). Statistically, they analyzed using four methods: partial least squares regression PLS, principal component regression PCR, multiple linear regression MLR, and principal component analysis PCA. The best QSPR modeling results are by PCR statistical analysis. It is proven by the validation results (R2 = 0.976; R2adj = 0.90) and analysis of collinearity in the data. The predictions of the four furan-derived compounds from PCR modeling gave promising results.

Tuning electronic structure and chemical reactivity via oxidation state in molybdenum oxide

Molybdenum oxide has a broad range of applications in areas such as catalysis, antimicrobial coatings, medicine, and sensors. In this study, we have investigated the geometric and electronic structure, thermal stability, and chemical reactivity of molybdenum oxide at different oxidation and electronic charge states using cluster models of Mo7On with density functional theory calculations. A decrease in the energy of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) has been identified as n increases from 0 to 21. Ionization potential and electron affinity of Mo7On correlate strongly with the energies of HOMO and LUMO, and both increase with increasing n. We have identified the most stable CO binding sites on Mo7On, calculated CO binding energy and simulated IR absorption spectrum of COMo7On. An n-dependent increase in CO stretching frequencies and decrease in CO binding energies indicate that electron backdonation from Mo7On to CO governs the changes in CO binding energy as a function of oxide composition. CO stretching frequency in COMo7O21 is 2197 cm−1, which is 55 cm−1 higher than in the gas phase CO molecule, indicating that CO is an electron density donor and the oxide acts as an electron acceptor at this stoichiometric composition. Comparing CO binding energies in neutral and ionic (q=+/-1) COMo7On, there is, in average, a stabilizing effect of excess (missing) charge on CO binding energy at low (high) n.

Designed and synthesized de novo ANTPABA-PDI nanomaterial as an acceptor in inverted solar cell at ambient atmosphere

In this work, a novel soluble and air-stable electron acceptor containing perylenediimide moiety named ANTPABA-PDI was designed and synthesized with band gap 1.78eV and that was used as non-fullerene acceptor material. ANTPABA-PDI possess not only good solubility but also much lower LUMO (lowest unoccupied molecular orbital) energy level. Furthermore, its excellent electron acceptor capability also supported by density functional theory calculation which validates the experimental observations. Inverted organic solar cell has been fabricated using ANTPABA-PDI along with P3HT as standard donor material in ambient atmosphere. The device, after characterization in open air, exhibited a power conversion efficiency of 1.70%. This is the first ever PDI based organic solar cell that has been fabricated completely in ambient atmosphere. The characterizations of the device have also been performed in ambient atmosphere. This kind of stable organic material can easily be used in fabricating organic solar cell and therefore it can be used as the best alternative as non-fullerene acceptor materials.

Nonpolar Cosolvent Driving LUMO Energy Evolution of Methyl Acetate Electrolyte to Afford Lithium‐Ion Batteries Operating at −60 °C

AbstractThe operation of lithium‐ion batteries (LIBs) at low temperatures (&lt;−20 °C) is hindered by the low conductivity and high viscosity of conventional carbonate electrolytes. Methyl acetate (MA) has proven to be a competitive low‐temperature electrolyte solvent with low viscosity and low freezing point, but its interfacial stability is poor and remains elusive until now. Here, it is revealed thaat the reductive stability of MA‐based electrolytes is fundamentally governed by the anion‐prevailed solvation structure. Based on this framework, fluorobenzene is employed in the electrolyte to promote the entry of anions into the solvation shell via dipole‐dipole interactions and the generation of free MA, thus enhancing the lowest unoccupied molecular orbital energy of MA. The designed electrolyte enables LiCoO2 (LCO)/graphite cells to exhibit excellent cycling performance at −20 °C (90% retention after 1000 cycles at 1 C) and to remain 91% of their room‐temperature capacity at a super‐low temperature of −60 °C at 0.05 C. Thanks to the plentiful free MA, this electrolyte has a high conductivity (2.61 mS cm−1) at −60 °C and allows LCO/graphite cell to charge at −60 °C. This study offers the possibility of practical applications for those solvents with poor reductive stability and provides new approaches to designing advanced electrolytes for low‐temperature applications.

Nonafluorobutane‐1‐Sulfonic Acid Induced Local High Concentration Additive Interface for Robust SEI Formation of High‐Voltage (5 V‐Class) Lithium Metal Batteries

AbstractTo optimize anode and cathode degradation issues in high‐voltage (5 V‐class) lithium metal batteries (LMBs), robust solid–electrolyte interfaces (SEI) on the surface of both anode and cathode are highly desired. Here, a nonafluorobutane‐1‐sulfonic acid (NFSA) additive is introduced to assist in the formation of the more stable and robust SEI to protect both anode and cathode. Typically, local high concentrations of lithium nonafluorobutane‐1‐sulfonate (NFSALi) and nonafluorobutane‐1‐sulfonate anion (NFSA−) could be achieved at the surface of anode and cathode respectively, through spontaneous chemical processes. The lowest unoccupied molecular orbital energy of NFSALi is lower and the highest occupied molecular orbital (energy of NFSA− is higher than electrolyte solvents. Thus, conformal and dense SEI passivation films are generated on the surface of both anode and cathode derived from electrochemical decomposition of NFSALi and NFSA−, respectively. Consequently, stable operation of Li metal anode and high‐voltage cathode are realized. The LiNi0.5Mn1.5O4(LNMO)//Li LMBs with NFSA‐containing electrolyte show great cycling stability with 93% capacity retention after 400 cycles and more stable Coulombic efficiency. This work specifies the double functions of NFSA as an interfacial layer forming additive to solve the degradation problems of high‐voltage (5 V‐class) LMBs, enabling high‐energy LMBs with significantly improved battery performance.

A rapid aroma quantification method: Colorimetric sensor-coupled multidimensional spectroscopy applied to black tea aroma

Aroma affects the quality of black tea, and the rapid evaluation of aroma quality is the key to realize the intelligent processing of black tea. A simple colorimetric sensor array coupled with a hyperspectral system was proposed for the rapid quantitative detection of key volatile organic compounds (VOCs) in black tea. Feature variables were screened based on competitive adaptive reweighted sampling (CARS). Furthermore, the performance of the models for VOCs quantitative prediction was compared. For the quantitative prediction of linalool, benzeneacetaldehyde, hexanal, methyl salicylate, and geraniol, the CARS–least-squares support vector machine model's correlation coefficients were 0.89, 0.95, 0.88, 0.80, and 0.78, respectively. The interaction mechanism of array dyes with VOCs was based on density flooding theory. The optimized highest occupied molecular orbital levels, lowest unoccupied molecular orbital energy levels, dipole moments, and intermolecular distances were determined to be strongly correlated with interactions between array dyes and VOCs.

A-DA′D-A Type Acceptor with a Benzoselenadiazole A′-Unit Enables Efficient Organic Solar Cells

A new A-DA′D-A structured narrow bandgap small molecular acceptor (SMA) Se46 was designed and synthesized by using benzoselenadiazole as the A′ unit and branched 2-butyloctyl as upper side chains in its DA′D central fused ring. It was found that Se46 shows red-shifted absorption compared to that of L8-BO with a benzothiadiazole A′ unit and an up-shifted lowest unoccupied molecular orbital energy level compared to that of Y6 with a benzothiadiazole A′ unit and linear n-C11H23 upper side chains. The organic solar cells (OSCs) based on PM6:Se46 demonstrate a high power conversion efficiency over 18% with an increased short circuit current density compared to that of the L8-BO-based devices and a higher open circuit voltage than that of the Y6-based devices. The results indicate that the synergetic modification of selenium substitution in the A′ unit and branched alkyl upper side chain is an effective strategy to further promote photovoltaic performance for the narrow bandgap A-DA′D-A type acceptors.

Pyrene derived imine functionalized moiety for highly selective colorimetric detection of Cu2+ ion real time sample with supportive DFT studies

Schiff base probe 4-hydroxy-N-(pyrene -1-yl-methylene) benzo hydrazide (PyrBH) has been synthesized and rationally designed as a rapid and highly selective colorimetric sensor for Cu2+ ions in the semi-aqueous medium. Structural characterization of PyrBH was confirmed by NMR, FT-IR, and HRMS spectral techniques. The cation binding affinity with the PyrBH probe was confirmed colorimetric study using the UV-Visible spectral method. The probe PyrBH exhibits a colorimetric response from colourless to yellow solutions containing Cu2+ ions. UV-Visible studies confirmed the formation of a 1:1 stoichiometry complex with a calculated binding constant Ka value (3.464 × 10-5 M) of suggests stable complex formation between the Cu2+ ions and the sensing PyrBH probe. The limit of detection (LOD) was found to be 2.19 × 10-7 M. The fabrication of test paper strips with the probe was done to detect the presence of Cu2+ ions in the real sample. The DFT & TD-DFT computational analysis was used to determine the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels, which it associates with satisfactory correlation.

A Novel Potassium Salt Regulated Solvation Chemistry Enabling Excellent Li-Anode Protection in Carbonate Electrolytes.

In lithium-metal batteries (LMBs), the compatibility of Li anode and conventional lithium hexafluorophosphate-(LiPF6 ) carbonate electrolyte is poor owing to the severe parasitic reactions. Herein, to resolve this issue, a delicately designed additive of potassium perfluoropinacolatoborate (KFPB) is unprecedentedly synthesized. On the one hand, KFPB additive can regulate the solvation structure of the carbonate electrolyte, promoting the formation of Li+ FPB- and K+ PF6 - ion pairs with lower lowest unoccupied molecular orbital (LUMO) energy levels. On the other hand, FPB- anion possesses strong adsorption ability on Li anode. Thus, anions can preferentially adsorb and decompose on the Li-anode surface to form a conductive and robust solid-electrolyte interphase (SEI) layer. Only with a trace amount of KFPB additive (0.03m) in the carbonate electrolyte, Li dendrites' growth can be totally suppressed, and Li||Cu and Li||Li half cells exhibit excellent Li-plating/stripping stability upon cycling. Encouragingly, KFPB-assisted carbonate electrolyte enables high areal capacity LiCoO2 ||Li, LiNi0.8 Co0.1 Mn0.1 O2 (NCM811)||Li, and LiNi0.8 Co0.05 Al0.15 O2 (NCA)||Li LMBs with superior cycling stability, showing its excellent universality. This work reveals the importance of designing novel additives to regulate the solvation structure of carbonate electrolytes in improving its interface compatibility with the Li anode.

Computational study of the role of counterions and solvent dielectric in determining the conductance of B-DNA.

DNA naturally exists in a solvent environment, comprising water and salt molecules such as sodium, potassium, magnesium, etc. Along with the sequence, the solvent conditions become a vital factor determining DNA structure and thus its conductance. Over the last two decades, researchers have measured DNA conductivity both in hydrated and almost dry (dehydrated) conditions. However, due to experimental limitations (the precise control of the environment), it is very difficult to analyze the conductance results in terms of individual contributions of the environment. Therefore, modeling studies can help us to gain a valuable understanding of various factors playing a role in charge transport phenomena. DNA naturally has negative charges located at the phosphate groups in the backbone, which provides both the connections between the base pairs and the structural support for the double helix. Positively charged ions such as the sodium ion (Na^{+}), one of the most commonly used counterions, balance the negative charges at the backbone. This modeling study investigates the role of counterions both with and without the solvent (water) environment in charge transport through double-stranded DNA. Our computational experiments show that in dry DNA, the presence of counterions affects electron transmission at the lowest unoccupied molecular orbital energies. However, in solution, the counterions have a negligible role in transmission. Using the polarizable continuum model calculations, we demonstrate that the transmission is significantly higher at both the highest occupied and lowest unoccupied molecular orbital energies in a water environment as opposed to in a dry one. Moreover, calculations also show that the energy levels of neighboring bases are more closely aligned to ease electron flow in the solution.