Solvent Coordination Research Articles

Low‐Solvent‐Coordination Solvation Structure for Lithium‐Metal Batteries via Electric Dipole‐Dipole Interaction

AbstractUnveiling inherent interactions among solvents, Li+ ions, and anions are crucial in dictating solvation‐desolvation kinetics at the electrode/electrolyte interface. Developing an electrolyte with a low ion‐transport barrier and minimal solvent coordination in its interfacial solvation structure is essential for forming an anion‐derived solid‐electrolyte interface, a key component for high‐performance Li‐metal batteries. In this study, we harness electric dipole‐dipole synergistic interactions to formulate an electrolyte with significantly reduced interfacial solvent coordination. Operando characterization and theoretical analysis reveal that 2‐fluoropyridine (FPy) with high dipole preferentially adsorbs onto the Li metal surface. The adsorbed FPy molecule squeezes succinonitrile in the primary solvation sheath through steric hindrance, leading to the formation of an inorganic‐rich interphase. Consequently, the introduction of FPy enhances the reversible capacity of the LiCoO2||Li cell, which maintains a capacity of 143 mAh g−1 after 500 cycles at a 1 C rate. Moreover, the cycle life of LiCoO2 batteries with a limited supply of lithium extends from 120 cycles to over 200 cycles. These findings offer a strategy that can be applied broadly to design interfacial solvation structures for various metal‐ion/metal‐based batteries.

Tuning solvation behavior within electric double layer via halogenated MXene for reliable lithium metal batteries

Solid electrolyte interphase (SEI)/electrolyte interface is critical in determining the lithium (Li) plating/stripping behavior. The solvation structure of Li-ion is well understood in the bulk electrolyte. Still, the mechanism of how SEI components affect the Li-ion solvation structure and desolvation energy barrier at the SEI/electrolyte interface is still unclear. Herein, Ti3C2 Maxine with single halogenated terminations (−Cl, −Br, −I) are synthesized and used as a model system, because their surface terminations induce a double halide-rich SEI formation (LiF and LiCl/LiBr/LiI). We examine the influence of the interaction strength between different Li halides and Li-ion on coordination number of Li ions and distribution of Li ions within the inner Helmholtz plane (IHP). A solvation sheath with a low solvent coordination number forms near the IHP of the LiBr interphase, improving the kinetics of Li deposition. Accordingly, half-cells utilising Li-carbon fiber/Ti3C2Br2 electrodes exhibit a long lifespan of 12,000 h (1 mA cm−2, 1 mAh cm−2). A pouch cell comprising Li-carbon fiber/Ti3C2Br2 anode and LiFePO4 cathode displays a capacity retention rate of 97 % after 300 cycles even at a low negative to positive electrode capacity ratio of 2.26. Our research provides crucial principles for the design of SEI components in Li metal batteries.

A molecular dynamics simulation study of EthylChlorophyllide A molecules confined in a SiO2 nanoslit.

This paper investigates the dynamic behavior of EthylChlorophyllide A (EChlideA) molecules in a methanol solution confined within a 4nm silica nanoslit, using molecular dynamics simulations over a duration of 1ms. Three systems, containing 1, 2, and 4 solutes, were studied at 298K. The results demonstrate that EChlideA molecules predominantly adsorb onto the silica surfaces, driven by specific interactions between chlorin ring's methyl group and the hydroxyl groups of the silica. This adsorption leads to stable binding, particularly in less crowded environments, as indicated by the potential of mean force analysis. Higher molecular concentrations, such as those with four EChlideA molecules, introduce variation in binding strength due to molecular aggregation and complex interactions. The orientation analysis reveals that the chlorin ring tends to align parallel to the surface, requiring rotational adjustments during surface diffusion. In addition, solvent coordination around the Mg ion remains consistent under bulk conditions, although with some variation in higher concentrations. This study also highlights a decrease in linear diffusion and an increase in rotational relaxation times for EChlideA molecules within the confined nanoslit, reflecting the influence of molecular concentration and arrangement on their dynamics. These findings provide valuable insights into the role of surface interactions, molecular orientation, and solvent coordination in confined environments, offering implications for the design of nanoscale systems.

Anionic Solvation Transition at Low Temperatures for Reversible Anodes in Lithium-Oxygen Batteries.

Li-O2 batteries provide a novel technology for electric energy storage due to their high energy density. However, the strong solvent coordination with Li+ at low temperatures impacts their performance and triggers irreversible interfacial reactions on the Li anode. Herein, cyclopentyl methyl ether (CME) is incorporated in a dimethoxyethane (DME)-based electrolyte to realize an anionic solvation transition at low temperatures in Li-O2 batteries. CME featuring a single O coordination site substitutes highly solvating DME in the first solvation sheath, and it induces more anion coordination to Li+ across the room- and low-temperature ranges. The low residence time of CME (66 ps at 25 °C, 382 ps at -40 °C.) in the solvation structures leads to the fast exchange of coordinated CME molecules with Li+ in comparison with DME and facilitates Li+ desolvation at low temperatures. The simultaneously generated inorganic-rich solid electrolyte interphase promotes Li+ transport to improve Li deposition and suppress Li dendrite formation. These enable the Li-O2 battery to present a good cycling stability of 110 cycles with a fixed capacity of 1000 mA h g-1 at -40 °C. This work paves the way for designing novel electrolytes in low-temperature batteries.

A Microscopically Heterogeneous Colloid Electrolyte for Extremely Fast-Charging and Long-Calendar-Life Silicon-Based Lithium-Ion Batteries.

Fast-charging capability and calendar life are critical metrics in rechargeable batteries, especially in silicon-based batteries that are susceptible to sluggish Li+ desolvation kinetics and HF-induced corrosion. No existing electrolyte simultaneously tackles both these pivotal challenges. Here we report a microscopically heterogeneous covalent organic nanosheet (CON) colloid electrolyte for extremely fast-charging and long-calendar-life Si-based lithium-ion batteries. Theoretical calculations and operando Raman spectroscopy reveal the fundamental mechanism of the multiscale noncovalent interaction, which involves the mesoscopic CON attenuating the microscopic Li+-solvent coordination, thereby expediting the Li+ desolvation kinetics. This electrolyte design enables extremely fast-charging capabilities of the full cell, both at 8 C (83.1 % state of charge) and 10 C (81.3 % state of charge). Remarkably, the colloid electrolyte demonstrates record-breaking cycling performance at 10 C (capacity retention of 92.39 % after 400 cycles). Moreover, benefiting from the robust adsorption capability of mesoporous CON towards HF and water, a notable improvement is observed in the calendar life of the full cell. This study highlights the role of microscopically heterogeneous colloid electrolytes in enhancing the fast-charging capability and calendar life of Si-based Li-ion batteries. Our work offers fresh perspectives on electrolyte design with multiscale interactions, providing insightful guidance for the development of alkali-ion/metal batteries operating under harsh environments.

A Microscopically Heterogeneous Colloid Electrolyte for Extremely Fast‐Charging and Long‐Calendar‐Life Silicon‐Based Lithium‐Ion Batteries

AbstractFast‐charging capability and calendar life are critical metrics in rechargeable batteries, especially in silicon‐based batteries that are susceptible to sluggish Li+ desolvation kinetics and HF‐induced corrosion. No existing electrolyte simultaneously tackles both these pivotal challenges. Here we report a microscopically heterogeneous covalent organic nanosheet (CON) colloid electrolyte for extremely fast‐charging and long‐calendar‐life Si‐based lithium‐ion batteries. Theoretical calculations and operando Raman spectroscopy reveal the fundamental mechanism of the multiscale noncovalent interaction, which involves the mesoscopic CON attenuating the microscopic Li+‐solvent coordination, thereby expediting the Li+ desolvation kinetics. This electrolyte design enables extremely fast‐charging capabilities of the full cell, both at 8 C (83.1 % state of charge) and 10 C (81.3 % state of charge). Remarkably, the colloid electrolyte demonstrates record‐breaking cycling performance at 10 C (capacity retention of 92.39 % after 400 cycles). Moreover, benefiting from the robust adsorption capability of mesoporous CON towards HF and water, a notable improvement is observed in the calendar life of the full cell. This study highlights the role of microscopically heterogeneous colloid electrolytes in enhancing the fast‐charging capability and calendar life of Si‐based Li‐ion batteries. Our work offers fresh perspectives on electrolyte design with multiscale interactions, providing insightful guidance for the development of alkali‐ion/metal batteries operating under harsh environments.

Synthesis and characterization of tetrapodal nickel complexes with adaptable ligand binding geometries.

This study explores the versatile binding properties of a tetrapodal ligand framework with nickel, demonstrating significant ligand fluxionality through the interconversions of several complexes. Kinetic studies using UV-vis and NMR techniques underscore the pivotal role of solvent coordination in initiating these dynamic processes. A unique reverse-dative Ni → Ag interaction provides another approach in modifying nickel's geometry.

Low-Solvent-Coordination Solvation Structure for Lithium-Metal Batteries via Electric Dipole-Dipole Interaction.

Unveiling inherent interactions among solvents, Li+ ions, and anions are crucial in dictating solvation-desolvation kinetics at the electrode/electrolyte interface. Developing an electrolyte with a low ion-transport barrier and minimal solvent coordination in its interfacial solvation structure is essential for forming an anion-derived solid-electrolyte interface, a key component for high-performance Li-metal batteries. In this study, we harness electric dipole-dipole synergistic interactions to formulate an electrolyte with significantly reduced interfacial solvent coordination. Operando characterization and theoretical analysis reveal that 2-fluoropyridine (FPy) with high dipole preferentially adsorbs onto the Li metal surface. The adsorbed FPy molecule squeezes succinonitrile in the primary solvation sheath through steric hindrance, leading to the formation of an inorganic-rich interphase. Consequently, the introduction of FPy enhances the reversible capacity of the LiCoO2||Li cell, which maintains a capacity of 143 mAh g-1 after 500 cycles at a 1C rate. Moreover, the cycle life of LiCoO2 batteries with a limited supply of lithium extends from 120 cycles to over 200 cycles. These findings offer a strategy that can be applied broadly to design interfacial solvation structures for various metal-ion/metal-based batteries.

Role of Solvent Coordination in the Multi-electron Redox Cycle of Nickel Diethyldithiocarbamate.

Nickel(II) diethyldithiocarbamate, NiII(dtc)2, is known to undergo a 2e- ligand-coupled electron transfer (LCET) oxidation to form [NiIV(dtc)3]+. However, the thermodynamics and kinetics of this 2e- process can be greatly affected by solvent coordination. For low coordinating solvents like acetonitrile and acetone, 2e- oxidation is observed via cyclic voltammetry (CV) at a single potential while stronger coordinating solvents like methanol, N,N-dimethylformamide, dimethyl sulfoxide, and pyridine exhibit a 1e- oxidation wave by formation of [NiIII(dtc)2(sol)x]+ intermediates. The decay of these complexes to eventually yield [NiIV(dtc)3]+ was monitored as a function of CV scan rate and temperature to extract rate constants and activation parameters. A thorough analysis of activation parameters revealed that ΔHapp⧧ generally increased with solvent coordination ability, suggesting solvent dissociation was a key factor in the rate limiting step. However, ΔSapp⧧ was found to be negative for all solvents, suggesting an associative mechanism in line with dimer formation with NiII(dtc)2 to facilitate ligand exchange. Density function theory calculations supported the competitive nature of dissociative and associative steps. Using these calculations, we propose two paths for decay of [NiIII(dtc)2(sol)x]+ species based on the coordination strength of the solvent. These studies point to the ability of solvents to either aid or hinder multielectron LCET reactions.

Thermodynamic and Kinetic Behaviors of Electrolytes Mediated by Intermolecular Interactions Enabling High-Performance Lithium-Ion Batteries.

Electrolyte solvation chemistry regulated by lithium salts, solvents, and additives has garnered significant attention since it is the most effective strategy for designing high-performance electrolytes in lithium-ion batteries (LIBs). However, achieving a delicate balance is a persistent challenge, given that excessively strong or weak Li+-solvent coordination markedly undermines electrolyte properties, including thermodynamic redox stability and Li+-desolvation kinetics, limiting the practical applications. Herein, we elucidate the crucial influence of solvent-solvent interactions in modulating the Li+-solvation structure to enhance electrolyte thermodynamic and kinetic properties. As a paradigm, by combining strongly coordinated propylene carbonate (PC) with weakly coordinated cyclopentylmethyl ether (CPME), we identified intermolecular interactions between PC and CPME using 1H-1H correlation spectroscopy. Experimental and computational findings underscore the crucial role of solvent-solvent interactions in regulating Li+-solvent/anion interactions, which can enhance both the thermodynamic (i.e., antireduction capability) and kinetic (i.e., Li+-desolvation process) aspects of electrolytes. Additionally, we introduced an interfacial model to reveal the intricate relationship between solvent-solvent interactions, electrolyte properties, and electrode interfacial behaviors at a molecular scale. This study provides valuable insights into the critical impact of solvent-solvent interactions on electrolyte properties, which are pivotal for guiding future efforts in functionalized electrolyte engineering for metal-ion batteries.

Molecular-docking electrolytes enable high-voltage lithium battery chemistries.

Ideal rechargeable lithium battery electrolytes should promote the Faradaic reaction near the electrode surface while mitigating undesired side reactions. Yet, conventional electrolytes usually show sluggish kinetics and severe degradation due to their high desolvation energy and poor compatibility. Here we propose an electrolyte design strategy that overcomes the limitations associated with Li salt dissociation in non-coordinating solvents to enable fast, stable Li chemistries. The non-coordinating solvents are activated through favourable hydrogen bond interactions, specifically Fδ--Hδ+ or Hδ+-Oδ-, when blended with fluorinated benzenes or halide alkane compounds. These intermolecular interactions enable a dynamic Li+-solvent coordination process, thereby promoting the fast Li+ reaction kinetics and suppressing electrode side reactions. Utilizing this molecular-docking electrolyte design strategy, we have developed 25 electrolytes that demonstrate high Li plating/stripping Coulombic efficiencies and promising capacity retentions in both full cells and pouch cells. This work supports the use of the molecular-docking solvation mechanism for designing electrolytes with fast Li+ kinetics for high-voltage Li batteries.

Quantum Chemical Interrogation of Reactions Promoted by Dirhodium Tetracarboxylate Catalysts─Mechanism, Selectivity, and Nonstatistical Dynamic Effects.

ConspectusRh2L4 catalysts have risen in popularity in the world of organic synthesis, being used to accomplish a variety of reactions, including C-H insertion and cyclopropanation, and often doing so with high levels of stereocontrol. While the mechanisms and origins of selectivity for such reactions have been examined with computational quantum chemistry for decades, only recently have detailed pictures of the dynamic behavior of reacting Rh2L4-complexed molecules become accessible. Our computational studies on Rh2L4 catalyzed reactions are described here, with a focus on C-H insertion reactions of Rh2L4-carbenes. Several issues complicate the modeling of these reactions, each providing an opportunity for greater understanding and each revealing issues that should be incorporated into future rational design efforts. First, the fundamental mechanism of C-H insertion is discussed. While early quantum chemical studies pointed to transition structures with 3-center [C-H-C] substructures and asynchronous hydride transfer/C-C bond formation, recent examples of reactions with particularly flat potential energy surfaces and even discrete zwitterionic intermediates have been found. These reactions are associated with systems bearing π-donating groups at the site of hydride transfer, allowing for an intermediate with a carbocation substructure at that site to be selectively stabilized. Second, the possible importance of solvent coordination at the Rh atom distal to the carbene is discussed. While effects on reactivity and selectivity were found to be small, they turn out not to be negligible in some cases. Third, it is shown that, in contrast to many other transition metal promoted reactions, many Rh2L4 catalyzed reactions likely involve dissociation of the Rh2L4 catalyst before key chemical steps leading to products. When to expect dissociation is associated with specific features of substrates and the product-forming reactions in question. Often, dissociation precedes transition structures for pericyclic reactions that involve electrons that would otherwise bind to Rh2L4. Finally, the importance of nonstatistical dynamic effects, characterized through ab initio molecular dynamics studies, in some Rh2L4 catalyzed reactions is discussed. These are reactions where transition structures are shown to be followed by flat regions, very shallow minima, and/or pathways that bifurcate, all allowing for trajectories from a single transition state to form multiple different products. The likelihood of encountering such a situation is shown to be associated again with the likelihood of formation of zwitterionic structures along reaction paths, but ones for which pathways to multiple products are expected to be associated with very low or no barriers. The connection between these features and reduced yields of desired products are highlighted, as are the means by which some Rh2L4 catalysts modulate dynamic behavior to produce particular products in high yield.

Inorganic fillers tailored Li+ solvation sheath for stable lithium metal batteries

Ionogel electrolytes based on gel scaffolds and ionic liquids (ILs) have garnered widespread attention for their processing compatibility, non-flammability, and exceptional thermal/electrochemical properties. While there have been many studies demonstrating the effectiveness of the bisalt approach in stabilizing lithium metal anode, the precise impact of skeleton-constrained dual-anion ionogels on interface modulation remains somewhat obscured and deserves further attention. Herein, we formulate a Li6.4La3Zr1.4Ta0.6O12 (LLZTO)-incorporated dual-anion ionogel to reveal the solvation chemistry in the presence of LLZTO and detail the Li+ transport mechanism and effect on the interfacial chemistries of Li-metal. The impact of inorganic substances on the solvation structure in IL-based solid electrolytes and their role in forming the SEI layer on lithium metal was unveiled. To be specific, the introduction of fillers exert a selective modulating influence on the anions species in the Li+-solvated shell and fine-tunes the local Li+ environment, thereby fostering a more robust interfacial layer. Modified ion environment in ionogels enables a preferable shift from vehicular to structural Li+ transport, whereby a high Li ion conductivity (1.24×10−3 S/cm) and high Li ion transference number of 0.42 is achieved. The synergistic solvent coordination and adjustment of the electrode-electrolyte interface enable the LiFePO4|PIL-10|Li cells to cycle steadily with capacity retention of 95.4 % after 500 cycles at 1C and 25 °C. The strategy of promoting transport mechanisms holds promise for designing the next-generation solid-state lithium metal batteries with high energy density.

Prominent Intrinsic Proton Conduction in Two Robust Zr/Hf Metal-Organic Frameworks Assembled by Bithiophene Dicarboxylate.

To date, developing crystalline proton-conductive metal-organic frameworks (MOFs) with an inherent excellent proton-conducting ability and structural stability has been a critical priority in addressing the technologies required for sustainable development and energy storage. Bearing this in mind, a multifunctional organic ligand, 3,4-dimethylthiophene[2,3-b]thiophene-2,5-dicarboxylic acid (H2DTD), was employed to generate two exceptionally stable three-dimensional porous Zr/Hf MOFs, [Zr6O4(OH)4(DTD)6]·5DMF·H2O (Zr-DTD) and [Hf6O4(OH)4(DTD)6]·4DMF·H2O (Hf-DTD), using solvothermal means. The presence of Zr6 or Hf6 nodes, strong Zr/Hf-O bonds, the electrical influence of the methyl group, and the steric effect of the thiophene unit all contribute to their structural stability throughout a wide pH range as well as in water. Their proton conductivity was fully examined at various relative humidities (RHs) and temperatures. Creating intricate and rich H-bonded networks between the guest water molecules, coordination solvent molecules, thiophene-S, -COOH, and -OH units within the framework assisted proton transfer. As a result, both MOFs manifest the maximum proton conductivity of 0.67 × 10-2 and 4.85 × 10-3 S·cm-1 under 98% RH/100 °C, making them the top-performing proton-conductive Zr/Hf-MOFs. Finally, by combining structural characteristics and activation energies, potential proton conduction pathways for the two MOFs were identified.

Suppression of potasside reaction in localized high concentration electrolytes utilizing fluorine-substituted benzene as bifunctional additive for potassium-metal batteries

Localized high-concentration electrolytes (LHCEs) have unique solvation structures that do not affect the original salt–solvent coordination from highly concentrated electrolytes. LHCEs enable a wide electrochemical voltage window and mitigate the extensive dendritic growth of metallic anodes. However, in K metal batteries, LHCE undergoes undesirable side reactions because of potasside (K−), triggering aggressive chemistry with a diluent, represented as hydrofluoroethers (HFEs), eventually resulting in poor cycle life. In this study, 1, 3, 5-trifluorobenzene (TFB) was introduced as a functional additive to prevent the parasitic K− reaction. The three symmetrically substituted fluorines prevented TFB from disrupting the as-formed solvation structure of LHCE located in the outer sphere. This characteristic increases the reaction energy barrier between K− and HFE, suppressing the deterioration of the metal anode by adding only 3 wt.% of TFB in LHCE. Moreover, TFB preferentially decomposes at each electrode because of its molecular energy level and increases the reversibility of the cell, reducing unnecessary consumption of electrolytes with a stable interface. This study discusses a novel method to prevent the K− reaction at the electrolyte level and the utilization of LHCE in K batteries to pursue higher energy densities, sustaining the advantage of using a metal anode.

Photochemistry of Ru(II) Triazole Complexes with 6-Membered Chelate Ligands: Detection and Reactivity of Ligand-Loss Intermediates.

Photochemical ligand release from metal complexes may be exploited in the development of novel photoactivated chemotherapy agents for the treatment of cancer and other diseases. Highly intriguing photochemical behavior is reported for two ruthenium(II) complexes bearing conformationally flexible 1,2,3-triazole-based ligands incorporating a methylene spacer to form 6-membered chelate rings. [Ru(bpy)2(pictz)]2+ (1) and [Ru(bpy)2(btzm)]2+ (2) (bpy = 2,2'-bipyridyl; pictz = 1-(picolyl)-4-phenyl-1,2,3-triazole; btzm = bis(4-phenyl-1,2,3-triazol-4-yl)methane) exhibit coordination by the triazole ring through the less basic N2 atom as a consequence of chelation and readily undergo photochemical release of the pictz and btzm ligands (ϕ = 0.079 and 0.091, respectively) in acetonitrile solution to form cis-[Ru(bpy)2(NCMe)2]2+ (3) in both cases. Ligand-loss intermediates of the form [Ru(bpy)2(κ1-pictz or κ1-btzm)(NCCD3)]2+ are detected by 1H NMR spectroscopy and mass spectrometry. Photolysis of 1 yields three ligand-loss intermediates with monodentate pictz ligands, two of which form through simple decoordination of either the pyridine or triazole donor with subsequent solvent coordination (4-tz(N2) and 4-py, respectively). The third intermediate, shown to be able to form photochemically directly from 1, arises through linkage isomerism in which the monodentate pictz ligand is coordinated by the triazole N3 atom (4-tz(N3)) with a comparable ligand-loss intermediate with an N3-bound κ1-btzm ligand also observed for 2.

Efficient Chemical Prelithiation with Modificatory Li+ Solvation Structure Enabling Spatially Homogeneous SEI toward High Performance SiOx Anode†

Comprehensive SummaryChemical prelithiation is widely proven to be an effective strategy to address the low initial coulombic efficiency (ICE) of promising SiOx anode. Though the reagent composition has been widely explored, the Li+ solvation structure, which practically plays the cornerstone role in the prelithiation ability, rate, uniformility, has rarely been explored. A novel environmentally‐friendly reagent with weak solvent cyclopentyl methyl ether (CPME) is proposed that enables both improved ICE and spatial homogeneous solid electrolyte interphase (SEI). And the prelithiation behavior and mechanism were explored focused on the Li+ solvation structure. Both theoretical investigation and spectroscopic results suggest that weak solvent feature of CPME reduces the solvent coordination number and decreases the Li+ desolvation energy. The optimized Li+ solvation structure enables high‐efficiency prelithiation that ensures the horizontal homogenization and mechanical properties of SEI. Moreover, the accompanied CPME molecules preferentially occupy positions in initial SEI, reducing the likelihood of LiPF6 decomposition and promoting longitudinal homogenization of SEI. Consequently, the efficient and homogenous prelithiation enables impressive ICE of 109.52% and improved cycling performance with 80.77% retained after 300 cycles via just 5 min soaking. Furthermore, the full cells with LiNi0.83Co0.12Mn0.05O2 (NCM831205) cathode display an enhancement in the energy density of 179.74% and up to 648.35 Wh·kg–1.

Minimal Coarse-Grained Models of Polar Solvent for Electrolytes: Stockmayer Versus Dumbbell.

This study explores the potential of the dumbbell solvent as a minimal model for understanding electrolyte solutions in polar solvents. Our investigation involves a comparative analysis of the dumbbell model and the Stockmayer model, focusing on ion solvation and ion-ion correlations. We examine electrolytes containing symmetric monovalent salts dissolved in polar solvents while varying the ion density and solvent polarity. Both models predict an augmented solvent coordination number around ions as the solvent polarity increases, with the dumbbell solvent displaying a more pronounced effect. Notably, radial distribution functions (RDFs) between solvent and ions yield differing trends; Stockmayer models exhibit a nonmonotonic relationship due to strong dipole-dipole interactions at higher polarity, while RDFs for ions and dumbbell solvents consistently rise. In response to increased solvent polarity, Stockmayer solvents within the ion's solvation shell undergo continuous dipole orientation shifts, whereas the dumbbell solvent predominantly adopts pointing-away dipole orientations, diminishing pointing-to orientations. This underscores the significance of the interplay between the solvent molecular orientation and dipole rotation. Both models qualitatively predict ion pairing and clustering behaviors across varying solvent dipole strengths and salt concentrations. The Stockmayer solvent generally provides stronger electrostatic screening than the dumbbell solvent due to its neglect of the coupling between molecular orientation and dipole rotation. What's more, at a high dipole moment regime, ion-ion correlations in Stockmayer solvent can become stronger with increasing dipole moment due to stronger solvent-solvent correlations. This study underscores the effectiveness of the dumbbell solvent model in systematically elucidating the fundamental principles governing electrolytes and offers potential applications in the rational design of electrolyte systems.

Solvatochromism of a saddle-distorted cationic Zn(II)-porphyrin complex

A saddle-distorted and cationic Zn(II)-porphyrin complex was revealed to exhibit solvatochromism in organic solvents, depending on the donor numbers. The color change was derived from the alteration of the HOMO-LUMO gap caused by the distortion of the porphyrin mean plane due to solvent coordination.

Exploring the Unusual Reactivity of the Hydrated Electron with CO2.

Many questions remain about the reactions of the hydrated electron despite decades of study. Of particular note is that they do not appear to follow the Marcus theory of electron transfer reactions, a feature that is yet to be explained. To investigate these issues, we used ab initio molecular dynamics (AIMD) simulations to investigate one of the better studied reactions, the hydrated electron reduction of CO2. The rate constant for the hydrated electron-CO2 reaction complex to react to form CO2- is for the first time estimated from AIMD simulations. Results at 298 and 373 K show the rate constant is insensitive to temperature, consistent with the low measured activation energy for the reaction, and the implications of this behavior are examined. The sampling provided by the simulations yields insight into the reaction mechanism. The reaction is found to involve both solvent reorganization and changes in the carbon dioxide structure. The latter leads to significant vibrational excitation of the bending and symmetric stretch vibrations in the CO2- product, indicating the reaction is vibrationally nonadiabatic. The former is estimated from the calculation of an approximate collective solvent coordinate and the free energy in this coordinate is determined. These results indicate that AIMD simulations can reasonably estimate hydrated electron reaction activation energies and provide new insight into the mechanism that can help illuminate the features of this unusual chemistry.