Highly concentrated electrolytes (HCEs) exhibit unique ion‐transport properties that fundamentally differ from those of conventional electrolytes; however, the role of anion species in governing Li+ transport remains unknown. Herein, Li+‐transport properties in lithium salt/propylene carbonate (LiX/PC) mixtures were systematically investigated by varying the basicity of the Lewis base anion: PF6−, N(SO2F)2−, N(SO2CF3)2−, ClO4−, BF4−, and SO3CF3− (TfO−). Ionic conductivity, viscosity, self‐diffusion coefficients, and Li+ transference numbers under anion‐blocking conditions were evaluated and correlated with molecular‐scale structures obtained from molecular dynamics simulations. Weak Lewis‐base anions exhibited high ionic conductivity and coupled Li+‐solvent diffusion at high salt concentrations. Conversely, strong Lewis‐base anions promoted ion‐pair and aggregate formation, resulting in structural diffusion of Li+ and high transference numbers. Notably, Li+ transference numbers increased with anion Lewis basicity and concentration, attaining 0.83 for LiTfO/PC = 1/2.5, while conductivity decreased, revealing an intrinsic tradeoff between these transport descriptors. Therefore, anion Lewis basicity critically governs ion association, correlated motion, and Li+‐transport mechanisms in HCEs.

Developing high‐performing photocatalysts and composites generate synergetic effects in modern photocatalysis. Zinc oxide (ZnO) is a promising photocatalyst; however, its wide bandgap and high charge carrier recombination rate significantly limit its visible‐light activity and overall photocatalytic efficiency. To overcome these challenges, this study focuses on the synthesis of Cu–Ag codoped ZnO/graphene nanocomposites using both hydrothermal and sonochemical methods, aiming to regulate the interfacial interaction and enhance charge separation. The hydrothermally synthesized (CAZ/Gr)H composite exhibited a lower bandgap, improved carrier transfer efficiency, and stronger Zn–O–C interfacial bonding compared to the sonochemically prepared (CAZ/Gr)S sample. Density functional theory (DFT) calculations confirmed the reduced work function and enhanced electron mobility in the hydrothermal system. Under natural sunlight, the (CAZ/Gr)H composite demonstrated superior photocatalytic degradation of organic dyes and excellent antibacterial activity against E. coli and S. aureus. These findings highlight the effectiveness of interface‐regulated, green‐synthesized ZnO‐based nanocomposites in addressing the fundamental limitations of traditional ZnO photocatalysts.

The Front Cover evokes particle swarm optimization applied to Bi–Pt bimetallic nanoparticles. Each bird represents a candidate nanoparticle structure. The lake and its shorelines represent the potential energy surface, generated using the ChiMES physics-informed machine learning potential. The surrounding mountains symbolize transition states, while the dark whirlpool at the lake’s center is the global energy minimum. More information can be found in the Research Article by N. T. Van-Oanh and co-workers (DOI: 10.1002/cphc.202500268).

The UV–Vis spectra of H2CO3 are investigated in a combined experimental and theoretical approach. A sample of solid H2CO3, prepared by electron irradiation of water–carbon dioxide ice, shows characteristics of both amorphous and crystalline H2CO3 in the infrared spectrum. To rationalize the experimentally observed redshift in the UV–Vis spectra between monomer and bulk H2CO3, a systematic computational study is devised using time‐dependent density functional theory. H2CO3 is investigated from the monomer to (H2CO3)n clusters, with n up to 66; in addition regular oligomer arrangements derived from previously proposed ambient‐pressure H2CO3 crystal structures are also examined. The calculations explain the UV–Vis absorption of solid carbonic acid, which is redshifted by ≈2 eV and ≈5 eV compared to the experimentally observed adiabatic ionization energy of the H2CO3 monomer. It is highlighted how these shifts emerge due to 1) increasing cluster size, 2) nonplanar arrangements, and 3) noncovalent interactions between H2CO3 chains and sheets. The study aims to establish spectrum‐to‐structure relationships and serves as computational reference data for astrochemical applications in the absence of experimental laboratory data of H2CO3 oligomers.

The scattering of NO molecules from a graphite surface has been investigated using molecular dynamics simulations in conjunction with a new potential energy surface that properly accounts for the basic role of long‐range interactions on the collision dynamics. NO molecules impinge the surface in selected low‐medium roto‐vibrational states with collision energies ranging from subthermal to hyperthermal. The initial vibrational state is preserved in the triggered elementary processes while the molecules scatter into rotational states that follow well‐defined distributions. For medium‐low values of the initial rotational state, molecules are mostly excited, whereas for medium values, there is a slight quenching effect. Moreover, for medium‐high collision energies, the rotational distributions reveal a unique feature: two secondary peaks appear in the region of final high rotational states. This phenomenon relates to the configuration of the molecule as it approaches the surface. Moreover, when NO molecules at low collision energy collide with the O‐end facing the surface, the scattering predominantly occurs through a direct mechanism. Conversely, when the N‐end is directed toward the surface, the scattering involves an indirect mechanism, characterized by multiple bounces on the surface, accompanied by significant energy exchanges between the molecular internal degrees of freedom and the surface itself.

Herein, it is shown that far‐infrared spectroscopy is a sensitive probe for detecting not only cation‐anion but also anion‐anion interaction in imidazolium‐based ionic liquids (ILs). The low‐frequency spectra of ILs with the same 1‐ethyl‐3‐methylimidazolium cation but different anions are measured, namely the acetate and glycinate anion, whereby the latter forms the simplest amino acid IL (AAIL). It is shown that two glycinate anions form two hydrogen bonds between either the carboxylate and amino groups allowing for attractive anion‐anion interaction despite the Coulomb repulsion between the ions of like charge. The spectral signature of the torsional motion of the amine groups ranges between 200 and 350 cm−1, strongly depending on the binding motif as determined by cation‐anion or anion‐anion interactions. This is confirmed by density functional theory calculations of frequencies of larger IL clusters exhibiting these characteristic binding motifs. The spectral signatures assigned to the cation‐anion interactions are correlated to measured enthalpies of vaporization, confirming a once proposed relation which can be obviously used for predicting thermodynamic properties from spectroscopy for less stable AAILs.

Calcium batteries (CaBs) fundamentally offer a promise of sustainable high energy density storage. However, the development of functional CaB electrolytes remains a key challenge. Here, molecular simulations are used to investigate structural and dynamic properties of solvent‐free molten salt electrolytes (MSEs) containing Ca2+ and alkali cations (Li+, Na+, K+), paired with either FSI or TFSI anions. Two equimolar MSEs, [Li, Na, K, Ca]FSI and [Li, Na, K, Ca] TFSI, are examined across a range of temperatures to better understand cation–anion interactions, coordination and local structure, and ion mobility, in particular with respect to Ca2+. The interplay between cation charge density, anion structure, and thermal effects provides valuable insights into the MSEs’ macroscopic behavior. These insights inform the design of advanced electrolytes that enhance Ca2+ mobility, supporting the development of next‐generation CaBs.

The Cover Feature illustrates chain fragments of a methacrylic copolymer with side-chain quinoline-based azo chromophores. Under UV/blue light illumination, the chromophores undergo trans–cis photoisomerization, adopting a bent conformation. In the dark, they revert via thermal cis–trans isomerization, resuming a linear shape. More information can be found in the Research Article by B. Derkowska-Zielinska and co-workers (DOI: 10.1002/cphc.202401155).

Differential capacitances (DCAPs) derived from electrostatic Gouy–Chapman‐type models for electrochemical double layers (DLs) typically show valley‐, bell‐, or camel‐type profiles as a function of the potential, centered around the potential of zero charge. These DCAP profiles are routinely evaluated with measured potential dependencies of capacitances. Here, the influences of hydrogen evolution, oxygen reduction, and oxide formation on the potential dependence of the capacitance of a polished gold electrode are experimentally examined. These parasitic reactions are found to cause most of the potential‐dependent capacitance features that are typically attributed to intrinsic DL properties. With these insights, the historical development of the literature regarding the development of the theoretical framework in relation to capacitance measurements is critically reevaluated. As a result, drawbacks of the 100‐year‐old Gouy–Chapman theory for the DL are identified. Moreover, DCAPs as differences of electrostatic states are discussed as unable to portray measured capacitances that result from capacitive–resistive and dynamic charge displacements in the DL. Hence, the links between theories and experiments are critically assessed, motivating the need for more advanced atomistic models to adequately portray the DL.

The Cover Feature shows the exploration of relativistic one- and four-component DFT methods for predicting hyperfine coupling constants in heavy heteroatom radicals. This study outlined in M. Witwicki’s Research Article (DOI: 10.1002/cphc.202400978) offers a practical blueprint for overcoming the computational challenges posed by these complex species, helping both computational chemists and experimentalists ascend the mountain range of difficulties and reveal the hidden electronic structure of heavy-element radicals.