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Simulating the dielectric spectra of solvents requires the nuanced definition of inter- and intra-molecular forces. Non-polarizable force fields, while thoroughly benchmarked for dielectric applications, do not capture all the spectral features of solvents, such as water. Conversely, polarizable force fields have been largely untested in the context of dielectric spectroscopy but include charge and dipole fluctuations that contribute to intermolecular interactions. We benchmark non-polarizable force fields and the polarizable force fields AMOEBA03 and HIPPO for liquid water and find that the polarizable force fields can capture all the experimentally observed spectral features with varying degrees of accuracy. However, the non-polarizable force fields miss at least one peak. To diagnose this deficiency, we decompose the liquid water spectra from polarizable force fields at multiple temperatures into static and induced dipole contributions and find that the peak originates from induced dipole contributions. Broadening our inquiry to other solvents parameterized with the AMOEBA09 force field, we demonstrate good agreement between the experimental and simulated dielectric spectra of methanol and formamide. To produce these spectra, we develop a new computational approach to calculate the dielectric spectrum via the fluctuation dissipation theorem. This method minimizes the error in both the low and high frequency portions of the spectrum, improving the overall accuracy of the simulated spectrum and broadening the computed frequency range. [ABSTRACT FROM AUTHOR]

The mutual synergistic regulation of the multi-functional sites on a single receptor molecule for ion-binding/recognition is vital for the new receptor design and needs to be well explored from experiment and theory. In this work, a new macrocyclic ion receptor (BEBUR) with three functional zones, including two ether holes and one biurea groups, is designed expecting to mutually enhance the ion-binding performance. The binding behaviors of BEBUR mainly for Cl− and Cs+ are deeply investigated by using density functional theoretical calculations. It is found that Cl−/Cs+ binding can be mutually enhanced and synergistically regulated via corresponding conformational changes of the receptor, well reflecting an electrical complementary matching and mutual reinforcement effect. Moreover, solvent effect calculations indicate that BEBUR may be an excellent candidate structure for Cl−-binding with the enhancement of counter ion (Cs+) in water and toluene. In addition, visualization of intermolecular noncovalent interaction is used for analysis on the nature of the binding interactions between receptor and ions. [ABSTRACT FROM AUTHOR]

Structures formed by dense CO adsorption layers can provide information about the balance between molecule–surface and molecule–molecule interactions. However, in many cases, the structure models are not clear. Using density functional theory (DFT) and scanning tunneling microscopy (STM), we have investigated the high-coverage CO layer on the Ru(0001) surface. Previous investigations by low-energy electron diffraction (LEED) and vibrational spectroscopy led to conflicting results about the structure. In the present study, 88 models with coverages between 0.58 and 0.77 monolayers have been analyzed by DFT. The most stable structures consist of small, compact CO clusters with an internal pseudo 1 × 1 structure. The CO molecules in the cluster centers occupy on-top sites in an upright position, whereas the molecules farther outside are slightly shifted from these sites and tilted outward. STM data of the CO-saturated surface at low temperatures, corresponding to a coverage of 0.66 monolayers, show a quasi-hexagonal pattern of features with an internal hexagonal fine structure. Simulated images based on the cluster model agree with the experimental data. It is concluded that the high-coverage CO layer consists of the close-packed clusters predicted by DFT as the most stable structure elements. In the experiment, the sizes and shapes of the clusters vary. However, the arrangement is not random but follows defined tiling rules. The structure remains ordered, almost up to room temperature. The LEED data are re-interpreted on the basis of the Fourier transforms of the STM data, solving the long-standing conflict about the structure. [ABSTRACT FROM AUTHOR]

Chromones are a class of naturally occurring compounds, renowned for their diverse biological activities with significant relevance in medicine and biochemistry. This study marks the first analysis of rotational spectra of both the chromone monomer and its monohydrate through Fourier transform microwave spectroscopy. The observation of nine mono-substituted 13C isotopologues facilitated a semi-experimental determination of the equilibrium structure of the chromone monomer. In the case of chromone monohydrate, two distinct isomers were identified, each characterized by a combination of O–H⋯O and C–H⋯O hydrogen bonds involving the chromone's carbonyl group. This study further delved into intermolecular non-covalent interactions, employing different theoretical approaches. The relative population ratio of the two identified isomers was estimated to be about 2:1 within the supersonic jet. [ABSTRACT FROM AUTHOR]

In this work, an energy decomposition analysis (EDA) method with the strategy of density matrix, called DM-EDA, is proposed on the basis of single reference electronic structure calculations. Different from traditional EDA methods, instead of an intermediate state wave function, the EDA terms in DM-EDA are expressed in the forms of the density matrix. This method can be carried out with various kinds of density matrices. With the efficient implementation, DM-EDA not only greatly improves the computational efficiency but also provides quantitative knowledge of intermolecular interactions with a large number of monomers. [ABSTRACT FROM AUTHOR]

A dynamic Monte Carlo (MC) method recently proposed by us [Nagai et al., J. Chem. Phys. 156, 154506 (2022)] to describe single-particle diffusion of a molecule in a heterogeneous space with position-dependent diffusion coefficient and free energy is generalized here to n-particle dynamics, where n molecules diffuse in heterogeneous media interacting via their intermolecular potential. Starting from the master equation, we give an algebraic proof that the dynamic MC transition probabilities proposed here produce particle trajectories that satisfy the n-particle diffusion equation with position-dependent diffusion coefficient D 0 i ( r i ) , free energy F 1 i ( r i ) , and intermolecular interactions Vij(ri, rj). The MC calculations based on this method are compared to molecular dynamics (MD) calculations for two-dimensional heterogeneous Lennard-Jones test systems, showing excellent agreement of the long-distance global diffusion coefficient between the two cases. Thus, the particle trajectories produced by the present MC transition probabilities satisfy the n-particle diffusion equation, and the diffusion equation well describes the long-distance trajectories produced by the MD calculations. The method is also an extension of the conventional equilibrium Metropolis MC calculation for homogeneous systems with a constant diffusion coefficient to the dynamics in heterogeneous systems with a position-dependent diffusion coefficient and potential. In the present method, interactions and dynamics of the real systems are coarse-grained such that the calculation cost is drastically reduced. This provides an approach for the investigation of particle dynamics in very complex and large systems, where the diffusing length is of sub-micrometer order and the diffusion time is of the order of milliseconds or more. [ABSTRACT FROM AUTHOR]

QM/MM methods have been used to study electronic structure properties and chemical reactivity in complex molecular systems where direct electronic structure calculations are not feasible. In our previous work, we showed that non-polarizable force fields, by design, describe intermolecular interactions through pairwise interactions, overlooking many-body interactions involving three or more particles. In contrast, polarizable force fields account partially for many-body effects through polarization, but still handle van der Waals and permanent electrostatic interactions pairwise. We showed that despite those limitations, polarizable and non-polarizable force fields can reproduce relative cooperativity achieved using density functional theory due to error compensation mechanisms. In this contribution, we assess the performance of QM/MM methods in reproducing these phenomena. Our study highlights the significance of the QM region size and force field choice in QM/MM calculations, emphasizing the importance of parameter validation to obtain accurate interaction energy predictions. [ABSTRACT FROM AUTHOR]

A new polymorph of 1,3-diacetylpyrene has been obtained from its melt and thoroughly characterized using single-crystal X-ray diffraction, steady-state UV-Vis spectroscopy and periodic density functional theory calculations. Experimental studies covered the temperature range from 90 to 390 K and the pressure range from atmospheric to 4.08 GPa. Optimal sample placement in a diamond anvil cell according to our previously presented methodology ensured over 80% data coverage up to 0.8 Å for a monoclinic sample. Unrestrained Hirshfeld atom refinement of the high-pressure crystal structures was successful and anharmonic behavior of carbonyl oxygen atoms was observed. Unlike the previously characterized polymorph, the structure of 2°AP-β is based on infinite π-stacks of antiparallel 2°AP molecules. 2°AP-β displays piezochromism and piezofluorochromism which are directly related to the variation in interplanar distances within the π-stacking. The importance of weak intermolecular interactions is reflected in the substantial negative thermal expansion coefficient of -55.8 (57) MK-1 in the direction of C-H...O interactions.

The intriguing network of antibody–antigen (Ab–Ag) interactions is highly governed by environmental perturbations and the nature of biomolecular interaction. Protein–protein interactions (PPIs) have potential applications in developing protein-adsorption-based sensors and nano-scale materials. Therefore, characterizing PPIs in the presence of a nanomaterial at the molecular level becomes imperative. The present work involves the investigation of antiferritin–ferritin (Ab–Ag) protein interactions under the influence of tungsten disulfide quantum dots (WS2 QDs). Isothermal calorimetry and contact angle measurements validated the strong influence of WS2 QDs on Ab–Ag interactions. The interfacial signatures of nano–bio-interactions were evaluated using sum frequency generation vibration spectroscopy (SFG-VS) at the air–water interface. Our SFG results reveal a variation in the tilt angle of methyl groups by ∼12° ± 2° for the Ab–Ag system in the presence of WS2 QDs. The results illustrated an enhanced ordering of water molecules in the presence of QDs, which underpins the active role of interfacial water molecules during nano–bio-interactions. We have also witnessed a differential impact of QDs on Ab–Ag by raising the concentration of the Ab–Ag combination, which showcased an increased inter-molecular interaction among the Ab and Ag molecules and a minimal influence on the methyl tilt angle. These findings suggest the formation of stronger and ordered Ab–Ag complexes upon introducing WS2 QDs in the aqueous medium and signify the potentiality of WS2 QDs relevant to protein-based sensing assays. [ABSTRACT FROM AUTHOR]

The topology of the Ehrenfest force field (EhF) is investigated as a tool for describing local interactions in molecules and intermolecular complexes. The EhF is obtained by integrating the electronic force operator over the coordinates of all but one electron, which requires knowledge of both the electron density and the reduced pair density. For stationary states, the EhF can also be obtained as minus the divergence of the kinetic stress tensor, although this approach leads to well-documented erroneous asymptotic behavior at large distances from the nuclei. It is shown that these pathologies disappear using the electron density functions and that the EhF thus obtained displays the correct behavior in real space, with no spurious critical points or attractors. Therefore, its critical points can be unambiguously obtained and classified. Test cases, including strained molecules, isomerization reactions, and intermolecular interactions, were analyzed. Various chemically relevant facts are highlighted: for example, non-nuclear attractors are generally absent, potential hydrogen–hydrogen interactions are detected in crowded systems, and a bifurcation mechanism is observed in the isomerization of HCN. Moreover, the EhF atomic basins are less charged than those of the electron density. Although integration of the EhF over regions of real space can also be performed to yield the corresponding atomic forces, several numerical drawbacks still need to be solved if electron density functions are to be used for that purpose. Overall, the results obtained support the Ehrenfest force field as a reliable descriptor for the definition of atomic basins and molecular structure. [ABSTRACT FROM AUTHOR]

Chemical and photochemical reactivity, as well as supramolecular organization and several other molecular properties, can be modified by strong interactions between light and matter. Theoretical studies of these phenomena require the separation of the Schrödinger equation into different degrees of freedom as in the Born–Oppenheimer approximation. In this paper, we analyze the electron–photon Hamiltonian within the cavity Born–Oppenheimer approximation (CBOA), where the electronic problem is solved for fixed nuclear positions and photonic parameters. In particular, we focus on intermolecular interactions in representative dimer complexes. The CBOA potential energy surfaces are compared with those obtained using a polaritonic approach, where the photonic and electronic degrees of freedom are treated at the same level. This allows us to assess the role of electron–photon correlation and the accuracy of CBOA. [ABSTRACT FROM AUTHOR]

Van der Waals clusters composed of He and aromatic molecules provide fundamental information about intermolecular interactions in weakly bound systems. In this study, phenol–helium clusters (PhOH–Hen with n ≤ 2) are characterized for the first time by UV and IR spectroscopies. The S1 ← S0 origin and ionization energy both show small but additive shifts, suggesting π-bound structures of these clusters, a conclusion supported by rotational contour analyses of the S1 origin bands. The OH stretching vibrations of the PhOH moiety in the clusters match with those of bare PhOH in both the S0 and D0 states, illustrating the negligible perturbation of the He atoms on the molecular vibration. Matrix shifts induced by He attachment are discussed based on the observed band positions with the help of complementary quantum chemical calculations. For comparison, the UV and ionization spectra of PhOH–Ne are reported as well. [ABSTRACT FROM AUTHOR]

The interfacial behavior of macromolecules dictates their intermolecular interactions, which can impact the processing and application of polymers for pharmaceutical and synthetic use. Using molecular dynamics simulations, we observe the evolution of a random heteropolymer in the presence of liquid–liquid interfaces. The system of interest forms single-chain nanoparticles through hydrophobic collapse in water, lacking permanent crosslinks and making their morphology mutable in new environments. Complex amphiphilic polymers are shown to be capable of stabilizing high interfacial tension water–hexane interfaces, often unfolding to maximize surface coverage. Despite drastic changes to polymer conformation, monomer presence in the water phase is generally maintained and most changes are due to increased hydrophobic solvent exposure toward the oil phase. These results are then compared to the behavior at the water–graphene interface, where the macromolecules adsorb but do not remodel. The polymer's behavior is shown to depend significantly on both its own amphiphilic character and the deformability of the interface. [ABSTRACT FROM AUTHOR]

Ion time-of-flight velocity-map imaging was used to measure the kinetic-energy distributions of the I2 ion-pair fragments formed after photoexcitation of Ar⋯I2 complexes to intermolecular vibrational levels bound within the Ar + I2 (E, vE = 0–2) potential energy surfaces. The kinetic-energy distributions of the I2 products indicate that complexes in the Ar⋯I2 (E, vE) levels preferentially dissociate into I2 in the D and β ion-pair states with no change in I2 vibrational excitation. The energetics of the levels prepared suggest that there is a non-adiabatic coupling of the initially prepared levels with the continuum of states lying above the Ar + I2 (D, vD = vE) and Ar + I2 (β, vβ = vE) dissociation limits. The angular anisotropies of the I2 product signals collected for many of the Ar⋯I2 (E, vE) levels have maxima parallel to the laser polarization axis. This contradicts expectations for the prompt dissociation of complexes with T-shaped geometries, which would result in images with maxima perpendicular to the polarization axis. These anisotropies suggest that there is a perturbation of the transition moment in these clusters or there are additional intermolecular interactions, likely those sampled while traversing above the attractive wells of the lower-energy potentials during dissociation. I2 (D′, vD′) products are also identified when preparing several of the low-lying levels localized in the T-shaped well of the Ar + I2 (E, vE = 0–2) potentials, and they are formed in multiple νD′ vibrational levels spanning energy ranges up to 500 cm−1. [ABSTRACT FROM AUTHOR]

The performance of sustainable polymers can be modified and enhanced by incorporating functional groups in the backbone of the polymer chain that increases intermolecular interactions, thus impacting the thermal properties of the material. However, in-depth studies on the role of intermolecular interactions on the crystallization of these polymers are still needed. This work aims to ascertain whether incorporating functional groups able to induce intermolecular interactions can be used as a suitable systematic strategy to modify the polymer thermal properties and crystallization kinetics. Thus, amide and additional ester groups have been incorporated into aliphatic polyesters (PEs). The impact of intermolecular interactions on the melting and crystallization behavior, crystallization kinetics, and crystalline structure has been determined. Functional groups that form strong intermolecular interactions increase both melting and crystallization temperatures but retard the crystallization kinetics. Selecting appropriate functional groups allows tuning the crystallinity degree, which can potentially improve the mechanical properties and degradability in semicrystalline materials. The results demonstrate that it is possible to tune the thermal transitions and the crystallization kinetics of PEs independently by varying their chemical structure. [ABSTRACT FROM AUTHOR]

Mass transfer through fluid interfaces is an important phenomenon in industrial applications as well as in naturally occurring processes. In this work, we investigate the mass transfer across vapor–liquid interfaces in binary mixtures using molecular dynamics simulations. We investigate the influence of interfacial properties on mass transfer by studying three binary azeotropic mixtures known to have different interfacial behaviors. Emphasis is placed on the effect of the intermolecular interactions by choosing mixtures with the same pure components but different cross-interactions such that different azeotropic behaviors are obtained. The molar flux is created by utilizing a non-stationary molecular dynamics simulation approach, where particles of one component are inserted into the vapor phase over a short period of time before the system's response to this insertion is monitored. From a direct comparison of the density profiles and the flux profiles in close proximity to the interface, we analyze the particles' tendency to accumulate in the interfacial region throughout the different stages of the simulation. We find that for mixtures with strong attractive cross-interactions, the inserted particles are efficiently transported into the liquid phase. For systems with weak attractive cross-interactions, the inserted particles show a tendency to accumulate in the interfacial region, and the flux through the system is lower. The results from this work indicate that the accumulation of particles at the interface can act as a hindrance to mass transfer, which has practical relevance in technical processes. [ABSTRACT FROM AUTHOR]

Biomolecular condensates can form through the liquid–liquid phase separation (LLPS) of proteins and RNAs in cells. However, other states of organization, including mesostructured network microstructures and physical gels, have been observed, the physical mechanism of which are not well understood. We use the Polymer Reference Interaction Site Model liquid state integral equation theory to study the equilibrium behavior of (generally aperiodic in sequence) biomolecular condensates based on a minimal sticker–spacer associating polymer model. The role of polymer packing fraction, sequence, and the strength and range of intermolecular interactions on macromolecular scale spatial organization and phase behavior is studied for typical sticker–spacer sequences. In addition to the prediction of conventional LLPS, a sequence-dependent strongly fluctuating polymeric microemulsion homogeneous state is predicted at high enough concentrations beyond the so-called Lifshitz-like point, which we suggest can be relevant to the dense phase of microstructured biomolecular condensates. New connections between local clustering and the formation of mesoscopic microdomains, the influence of attraction range, compressibility, and the role of spatial correlations across scales, are established. Our results are also germane to understanding the polymer physics of dense solutions of nonperiodic and unique sequence synthetic copolymers and provide a foundation to create new theories for how polymer diffusion and viscosity are modified in globally isotropic and homogeneous dense polymeric microemulsions. [ABSTRACT FROM AUTHOR]

The synthesis of charge assisted amidinium...phosphonate hydrogen-bonded organic frameworks (HOFs) is reported. Two tectons, with either a biphenyl or naphthalene diimide backbone, were combined with bis-amidinium salts to afford HOF1 and HOF2, respectively. Whereas HOF1 formed rapidly, typically within two days of mixing, HOF2 proved more challenging to synthesise. Interestingly, the presence of sunlight facilitated the rapid formation of HOF2 within a few hours. Although crystals of tectons 1H4 or 2Et4 exhibited densely packed structures, combination of the corresponding phosphonate bases with bisamidinium cations, through amidinium...phosphonate interactions, gave open framework materials. The HOFs formed through this approach exhibited notable stability limitations, including a propensity for phase transformations or structural collapse upon solvent removal. [ABSTRACT FROM AUTHOR]

A new palladium(II) complex containing the previously synthesized 4,10-bis[(3-hydroxy-4-pyron-2-yl)methyl]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane ligand maltonis was prepared and characterized both in solution and in the solid state. Hirshfeld surface and energy framework analyses were also performed. Because maltonis already showed antineoplastic activity, the complexation of Pd(II), chosen as an alternative to Pt(II), was investigated to study its possible biological activity. UV-vis and NMR studies confirmed the formation and stability of the complex in aqueous solution at physiological pH. X-ray diffraction data revealed a structure where the Pd(II) ion is lodged in the dimethyl-cyclen cavity, with maltol rings facing each other (closed shape) even if they are not involved in the coordination. DFT analysis was performed in order to understand the most stable shape of the complex. In view of evaluating its possible bioactive conformation, the DFT study suggested a slight energetic preference for the closed one. The resulting closed complex was stabilized in the X-ray structure by intermolecular interactions that replace the intramolecular interactions present in the optimized complex. According to the DFT calculated formation energies, notwithstanding its rarity, the Pd(II) complex of maltonis is the thermodynamically preferred one among analogous complexes containing different metal ions (Pt(II), Co(II), and Cu(II)). Finally, to study its possible biological activity, the interaction between the Pd(II) complex of maltonis and nucleosides was evaluated through NMR and DFT calculations, revealing a possible interaction with purines via the maltol moieties. [ABSTRACT FROM AUTHOR]

Two phenothiazine derivatives, PTCNB and PTCNTBB, were designed and synthesized to confirm whether triaryl-substituted phenothiazine has mechanofluorochromic (MFC) properties and investigate the impact of tert-butyl (t-butyl) as a steric hindrance group on the molecular response to force stimuli. It was observed that the introduction of the t-butyl moiety did not significantly alter the molecular photophysical properties in the solution state due to its minimal effect on molecular π-conjugation. However, the presence of t-butyl strongly influenced their photoluminescence behavior and force-stimulus response in the solid state. PTCNB without t-butyl exhibited orange fluorescence in its pristine solid, which transformed into red fluorescence upon grinding, accompanied by a spectral shift of 23 nm. Conversely, PTCNTBB with t-butyl displayed green fluorescence in the as-synthesized solid and subsequently emitted orange fluorescence under force stimuli, demonstrating a more pronounced color variation. The corresponding spectral shift value was measured to be 58 nm. Remarkably, both ground solids regained their original fluorescence colors after vapor fuming, indicating a reversible MFC process. XRD patterns suggested that the application of force stimuli disrupted the intermolecular ordered packing while the fuming process restored ordered stacking, leading to the recovery of fluorescence emission. Absorption spectral changes implied that the presence of t-butyl induced loose packing and weak π--π interactions in PTCNTBB's initial solid, resulting in a short-wavelength fluorescence. Under force stimuli, the intermolecular interaction between PTCNTBB molecules was significantly enhanced, leading to an obvious redshift in the fluorescence spectra. In contrast, due to the absence of bulky steric groups, intermolecular packing between PTCNB molecules was relatively dense in its pristine solid and then applying pressure did not cause significant changes in a π-packing arrangement; hence only a small spectral shift occurred. [ABSTRACT FROM AUTHOR]

Two sets of co-formers, polyfluorinated arylenediamines with variable structural elements and macrocyclic ethers of different sizes, were used to study the patterns of self-assembly of co-crystals and to rank the intermolecular interactions. The co-crystallization stoichiometry was found to increase from 1 : 1 to 2 : 1 in the series trifluoro-1,3-phenylenediamine, 2,4-diaminotrifluoropyridine, and 2,4-diaminotrifluoronitrobenzene and with decreasing crown ether size due to restructuring of guest--host interactions and forming guest-guest interactions. 18-Crown-6 and 15-crown-5 ethers form the typical N--H...Ocr H-bonds connecting two Ocr atoms with one bifunctional proton donor NH2; when going to 12-crown-4, two Ocr atoms become connected with the Hamino atoms of two arylenediamine molecules. Modes of guest--guest bonding and supramolecular motifs in 2 : 1 co-crystals are determined by HB acceptors and p + π systems in arylenediamine: o-N--H...Nhet and p-N--H...F interactions form face-to-face dimers united in a chain; p-N-H...Onitro and o-N--H...Onitro contacts generate head-to-tail and head-to-side chains; π...π and X...π (X = F, O, N) electron interactions form off-set stacks. Quantum chemical calculations reveal an increase of the packing enthalpies and bonding energies with increasing arylenediamine electron affinity and crown ether size. According to MEP, BCP and NCI analyses, these effects are caused either by strengthening of the interactions due to a greater electrostatic contribution, or by multiplying bonding contacts. Quantifying the interactions allowed us to identify the key supramolecular synthons and related elements of the co-former structure, which can serve as tools in the molecular crystal design. [ABSTRACT FROM AUTHOR]

The gelation of two TADF positional isomers, 4BPy-mDTC and BPy-DTC, was explored. Among these emitters, only 4BPy-mDTC forms stable organogels due to the optimized intermolecular interactions. Interestingly, the morphology of the gel can be tuned from fibre to fettuccine by changing the solvents. The electrical conductivity of the self-assembly can also be increased from 8.05 × 10−4 S m−1 to 6.05 × 10−3 S m−1 by tuning the morphology. [ABSTRACT FROM AUTHOR]

BACKGROUND: The present study aimed to determine how various amounts (0.00, 0.58, 1.52 and 4.50 g 100 g−1) of wine lees (WL), which contains numerous essential components, impact the emulsifying properties of fish gelatin (FG) at a low concentration (0.5 g 100 g−1) in the high‐fat phase (65 g 100 g−1). This study conducted rheology, physicochemical technical and characterization analyses on the emulsions to provide sustainable and innovative approaches for spreadable oils. RESULTS: The addition of WL to FG emulsions improved oxidative stability, emulsion stability and bioactive compounds. The zeta potential (−101 ± 5.62 mV) of 0.58 g 100 g−1 WL‐containing emulsion (PE1) was found to be high, whereas particle size (347.6 ± 5.25 nm) and polydispersity index (0.50) were statistically low. It was also found that the addition of WL improved the intermolecular interactions, crystallinity and microstructural properties of the emulsions. All these results were supported by simulating the molecular configuration between FG and WL. The compounds gallic acid, caffeic acid, myricetin, quercetin and resveratrol showed a strong affinity to FG, with free binding energies of −5.50, −5.88, −6.53, −6.68 and −6.66 kcal mol−1, respectively. CONCLUSION: As a result, WL‐supported FG has the potential to be used as an alternative to egg proteins to develop sustainable low‐cost spreadable emulsions. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Adsorption of H2 on a bed of NaBr for the formation of NaBr(H2)n (n = 1–8) aggregates is reported here theoretically. Second-order Moller–Plesset perturbation calculations were carried out using the MP2/aug-cc-pVDZ level for predictions of adsorption energies and Gibbs free energy changes for these aggregates. The NaBr(H2)n aggregates are predicted to steadily increase in H2 saving capacity and energy efficiency as n increases from 1 to 8, relative to free H2 molecules under identical conditions. The low activation energies for H2 desorption from the NaBr(H2)n adducts result in high amounts of H2 molecules desorbed at low temperatures. The vibrational stretching frequencies of H2 (H–H) show a red shift. The Natural Bond Orbital calculations were used to investigate the nature of NaBr···H2 interactions. Furthermore, cooperativity was predicted as a result of the stabilization energy of complexes and is discussed. Finally, electronic properties of the NaBr(H2)n clusters were obtained by the density of states calculation. [ABSTRACT FROM AUTHOR]

Complex formulations based on poly(hydroxybutyrate) (PHB) and poly(hydroxybutyrate-co-valerate) (PHBV) were studied to statistically assess the effect of formulation (i.e., hydroxyvalerate (HV) content, plasticiser chemistry and content, filler type and content) on their thermal properties and degree of crystallinity (Xc). In binary systems, thermal properties were mainly influenced by filler type rather than its content, while for plasticised systems the changes were dependent on both increasing plasticiser content and PHB-plasticiser compatibility. Variations in HV content affected the ability of the polymer chain to fold, leading to significant changes in both thermal properties and Xc. In ternary systems, presence of multiple additives and consequent changes in intermolecular interactions lead to multifaceted behaviours that were not easily predicted by results from binary systems alone. For example, melting temperature did not show dependence on filler presence in PHBV systems despite introducing variations in pure PHB systems. In general, thermal properties and Xc are affected by all parameters studied, with changes in system free volume (i.e. changes in HV content and plasticisation) playing the most significant role. These results expand the understanding of factors controlling crystallisation in complex polymer systems and can be used to control matrix properties in new generations of packaging materials. [ABSTRACT FROM AUTHOR]

Recently, an ever‐growing interest has been paid on organic single‐molecule white light‐emitting materials for effective white organic light‐emitting diodes (WOLEDs). However, subject to Kasha's rule, photons can only be emitted from the lowest excited state and thus panchromatic or dual emissions are extremely forbidden, which results in a certain challenge in achieving white emission. Herein, a strategy of synergetic carbonyl and heptagonal structure is proposed for organic single‐molecule white light emission and demonstrated by TAO/TABO/TA2O organic luminescent materials that are modified on aryl ketones/amine fragments. Among them, due to the robust intermolecular interactions triggered by synergetic carbonyl and heptagonal structure, TA2O exhibits vibrant monomer and dimer photoluminescence with dual thermally activated delayed fluorescence (TADF) characteristics. As a result, the first single‐molecule dual‐TADF WOLED based on the synergetic system is successfully fabricated with an external quantum efficiency of 7.2%. This study not only expands the scope of carbonyl and heptagonal structure for novel optoelectronic properties and applications but also opens new avenues for the development of efficient single‐molecule WOLEDs with dual TADF mechanisms. [ABSTRACT FROM AUTHOR]

Flexible organic crystal materials with optical waveguide property have attracted much attention for various applications. Meanwhile, the rising demand for deep space and polar explorations have brought about a growing interest in materials with low temperature flexibility. However, the development of organic crystal materials integrating optical waveguide and low temperature elasticity remains a significant challenge. Here, three flexible organic crystals with bromo‐hydroxy chalcone backbone are developed via molecular engineering strategy. The 4BHIE crystal with 4‐bromo‐N‐ethyl substituent exhibits superior 2D elasticity under mechanical external forces with ≈180° bending and 1.30 mm of curvature. The low optical loss coefficient of only 0.309 dB mm−1 also demonstrates potential applications in flexible optoelectronic waveguides. Interestingly, the introduction of a longer alkyl chain onto N atom of indole moiety (4BHIB) exhibits more remarkable flexibility with 0.35 mm of curvature due to its richer and more complex network of intermolecular interactions compared with that of 4BHIE. Furthermore, 5BHIE crystal with 5‐bromo‐N‐ethyl substituent shows not only elasticity at room temperature but also low‐temperature elasticity in liquid nitrogen with reversible temperature response owing to the strengthening intermolecular interactions at low temperature. 5BHIE crystal displays potential optical waveguide application in low temperature environments. [ABSTRACT FROM AUTHOR]

Small molecule organic materials have been considered promising candidates as cathodes in aqueous zinc‐ion batteries (AZIBs) because of their low cost, environmental friendliness, and sustainable production. However, the rapid capacity fading and sluggish kinetics restrict their practical applications, especially under extremely low temperatures (−50 °C). Here, by the condensation of hexaketocyclohexane octahydrate (HKCO) and 1, 2‐diaminoanthraquinone (DQ), a fully conjugated organic molecule, anthraquinone‐quinoxaline derivative (HATAN) is prepared. With the fully conjugated structure, HATAN possesses enhanced π‐electron delocalization and strong intermolecular interaction, which ensure superior electronic conductivity and physicochemical/electrochemical stability. Additionally, the introduction of multiple redox‐active sites (C═O and C═N) can increase the theoretical capacity of HATAN. Consequently, the HATAN cathode for AZIBs exhibits remarkable capacity, long lifespan, and high‐rate capability. Even at −50  C, an exceptional capacity of 75.4 mAh g−1 and 98% capacity retention over 1500 cycles can be preserved. This study presents valuable insights into the structure design of small molecule organic cathodes for advanced AZIBs which can efficiently operate at −50 °C. [ABSTRACT FROM AUTHOR]

Two new 1,3-dicarbonyl compounds bearing an o-hydroxyphenyl moiety (for short, I and II) were synthesized and subjected to structural, experimental and theoretical studies. Vibrational spectroscopy (IR and Raman) and X-ray diffraction were used for solid phase studies, while NMR and electron spectroscopy allowed analysis in solution. The crystal structures of I and II, determined by X-ray diffraction methods, are closely related to each other (rms deviation of homologous atoms from their best fit is 0.147 Å). The observed planarity of β-hydroxyphenylcarbonyl enols fragment in the compounds is enforced by both extended π-bonding and intramolecular OH⋯O bonds. Molecules in I are arranged in the lattice as center-symmetric dimers held by relatively weak intermolecular OH⋯O bonds. Hirshfeld surface (HS) analysis, atoms in molecules (QTAIM), and natural bonding orbitals (NBO) approaches were employed to study theoretically selected dimers constructed from X-ray data. The results were combined with experimental ones to obtain deep insight into the strength and type of intermolecular interactions. A chalcogen bond interaction was detected in I. Although the O⋯O interaction is unusual, it participates in the attractive forces that stabilize the crystal lattice. The title compounds are present in the solid state only as the keto–enol tautomer, while in solution the diketo tautomer is also detected at concentrations of 5%. In vitro studies showed that I have better antimicrobial properties than II, mainly against the S. aureus strain. [ABSTRACT FROM AUTHOR]

Vibration and noise severely affect the operation of mechanical equipment and is also detrimental to human health. Therefore, the development of high performance damping materials is crucial. However, current methods to improve damping properties often come at the expense of mechanical properties, resulting in inferior mechanical performance of materials. In order to address the issue of imbalance between damping properties and mechanical properties in polyurethane damping elastomers. In this study, polyester dangling chains containing polar groups are synthesized and introduced into polyurethane. The obtained polyurethane exhibited an effective damping temperature range of 154 °C (−54 °C to 100 °C) and a tensile strength of 15.82 MPa. Furthermore, dynamic mechanical analysis and broadband dielectric relaxation spectroscopy are combined to investigate the influence of polar dangling chains on the structure and properties of polyurethane. The degree of microphase separation increases after the introduction of polar dangling chains, indicating enhances intermolecular interaction forces, facilitating the formation of hydrogen bond between the main chain and dangling chains, thereby increasing molecular chain friction and energy dissipation. This work overcomes the challenge of balancing the damping and mechanical properties of polyurethane, providing a new strategy for designing high performance polyurethane damping elastomers. [ABSTRACT FROM AUTHOR]

Molecules in the bulk state are typically constrained by multiple intermolecular interactions, making it challenging to develop emission‐tunable solid‐state materials. Manipulating molecular motion is essential for achieving dynamic solid‐state emissions. Herein, various emission‐tunable 4CN@polymer films are developed whose multicolor luminescence arises from different molecular motion modes within the polymer microenvironments. There are three motion modes in the films: restricted, normal, and vigorous. In the normal mode, the film emits green light, shifting to purple under UV (515–387 nm). Cooling or fuming creates a rigid environment, leading to blue emission at 426 nm. High temperatures induce vigorous motion, causing quenched emission, which can be reactivated by cooling. This mechanism underscores the significant influence of molecular motion within flexible polymers on the luminescence behavior of 4CN@polymer films, enabling multicolor emission based on environmental conditions. The wide‐range fluorescence—from purple, blue, white, green, yellow‐green to dark—indicates promising applications in multifaceted dynamic displays and information security. This study offers novel perspectives on the correlation between solid‐state molecular motion and dynamic emission. [ABSTRACT FROM AUTHOR]

Material design based on the assembly of functional units has demonstrated tremendous technical and commercial potential. Among others, polymers are identified to be an ideal building block due to their abundant functional groups, high programmability, and great biocompatibility. In this review, introducing recently developed advanced materials enabled by rationally designed polymer self‐assembly are focussed. The working principle of typical intermolecular interactions to shape nano‐patterns and structural heterogeneity is first explained in detail. Following that, methods to prepare advanced materials and their characteristic properties are discussed. The superior performance of polymer assemblies renders numerous potential applications in ultra‐tough devices, soft robotics, electronics, sensors, and biomedicine. A brief account of representative examples is highlighted and a perspective on this field is provided at the end. [ABSTRACT FROM AUTHOR]

The application of supramolecular assembly (SA) with room temperature phosphorescence (RTP) in aqueous phase has the potential to revolutionize numerous fields. However, using simple molecules with crystalline RTP to construct SA with aqueous phase RTP is hardly possible from the standpoint of forces. The reason lies in that the transition from crystal to SA involves a structure transformation from highly stable to more dynamic state, leading to increased non‐radiative deactivation pathways and silent RTP signal. Here, with the benefit of the confinement from the layered double hydroxide (LDH), various simple molecules (benzene derivatives) can successfully form metastable SA with aqueous phase RTP. The maximum of RTP lifetime and efficiency can reach 654.87 ms and 5.02 %, respectively. Mechanistic studies reveal the LDH energy trap can strengthen the intermolecular interaction, providing the prerequisite for the existence of metastable SA and appearance of aqueous phase RTP. The universality of this strategy will usher exploration into other multifunctional monomer, facilitating the development of SAs with aqueous phase RTP. [ABSTRACT FROM AUTHOR]

Passivation of perovskite crystals is a crucial strategy to improve the efficiency and stability of perovskite solar cells (PSCs). Zwitterions, which contain both positive and negative charges in the molecule, can be used to passivate perovskite crystals. However, these materials strongly interact with each other, resulting in extremely low solubility in common organic solvents. The low solubility of zwitterions hinders the formation of uniform films, which negatively affects perovskite crystal growth. In this study, a liquid‐type zwitterion (LTZ) is synthesized by modulating intermolecular interactions of the zwitterion (3‐(1‐Pyridinio)‐1‐propanesulfonate). By suppressing intermolecular interactions, the solubility and processibility of the zwitterion in common organic solvents are successfully improved. The well‐distributed LTZ‐treated films are obtained, resulting in better electrical properties for the PSCs compared to solid‐type zwitterion‐based devices. With these characteristics, the resulting device achieves a power conversion efficiency of 24.9% with excellent thermal stability (under 60 °C and N2 atmosphere), maintaining over 80% of its initial efficiency for 1968 h. In addition, the PSC module (active area of 32.7 cm2) achieves an improved efficiency of 19.86% with high open‐circuit voltage and fill factor. The results suggest that interface engineering with an LTZ has the potential to fabricate efficient and stable PSCs. [ABSTRACT FROM AUTHOR]

A new type of material, organic salts in the crystal and crystalline powder state, with both excitation wavelength dependent (Ex‐De) fluorescence and Ex‐De phosphorescence under ambient conditions have been reported. The single component triphenylsulfonium chloride displays tunable fluorescent colors ranging from light purple to sky blue and tunable afterglow colors varying from green to yellowish green, to yellow (lifetimes: 57, 141, 66 ms, afterglow lasting for 2.1, 2.0, 2.3 s). The relationship between the structure and luminescence performance of 17 sulfonium salt derivatives confirms the pivotal roles of both the anions and the electronic and steric effect of substituent factors for luminescence. Single‐crystal analysis reveals that unique ionic bonding and intermolecular interaction can promote an ordered arrangement of organic salts in a crystal state, which then can facilitate molecular aggregation for phosphorescence generation. Theoretical calculations have also confirmed this viewpoint. More importantly, these sulfonium salt derivatives can be used for advanced multimodal anti‐counterfeiting and mitochondrial imaging, respectively. This study has not only expanded the scope of Ex‐De materials but also extended their applications. [ABSTRACT FROM AUTHOR]

The structure of molecular aggregates is crucial for charge transport and photovoltaic performance in organic solar cells (OSCs). Herein, the intermolecular interactions and aggregated structures of nonfused‐ring electron acceptors (NFREAs) are precisely regulated through a halogen transposition strategy, resulting in a noteworthy transformation from a 2D‐layered structure to a 3D‐interconnected packing network. Based on the 3D electron transport pathway, the binary and ternary devices deliver outstanding power conversion efficiencies (PCEs) of 17.46 % and 18.24 %, respectively, marking the highest value for NFREA‐based OSCs. [ABSTRACT FROM AUTHOR]

A variety of therapeutic possibilities have emerged for skillfully regulating protein function or conformation through intermolecular interaction modulation to rectify abnormal biochemical reactions in diseases. Herein, a devised strategy of enzyme coordinators has been employed to alleviate postoperative pancreatic fistula (POPF), which is characterized by the leakage of digestive enzymes including trypsin, chymotrypsin, and lipase. The development of a dextrorotary (D)-peptide supramolecular gel (CP-CNDS) under this notion showcases its propensity for forming gels driven by intermolecular interaction. Upon POPF, CP-CNDS not only captures enzymes from solution into hydrogel, but also effectively entraps them within the internal gel, preventing their exchange with counterparts in the external milieu. As a result, CP-CNDS completely suppresses the activity of digestive enzymes, effectively alleviating POPF. Remarkably, rats with POPF treated with CP-CNDS not only survived but also made a recovery within a mere 3-day period, while mock-treated POPF rats had a survival rate of less than 5 days when experiencing postoperative pancreatic fistula, leak or abscess. Collectively, the reported CP-CNDS provides promising avenues for preventing and treating POPF, while exemplifying precision medicine-guided regulation of protein activity that effectively targets specific pathogenic molecules across multiple diseases. Therapeutic possibilities have emerged for rectifying abnormal biochemical reactions by modulating intermolecular interactions. Here, the authors present a regulatory strategy for capturing biomolecules and preventing enzyme leakage using a chiral-engineered peptide supramolecular gel. [ABSTRACT FROM AUTHOR]

All‐polymer solar cells (all‐PSCs) offer promising potential for large‐scale manufacturing due to their remarkable mechanical and thermal stability. However, the limited capacity of polymer acceptors for near‐infrared (NIR) photon harvesting has impeded their progress in semi‐transparent (ST) all‐PSCs. Here, the study develops a pair of new NIR polymer acceptors, named PYSeF‐T and PYSe2F‐T, with mono‐/di‐fluorinated end groups capped to the selenide monomer backbone, respectively. Owing to the stronger intermolecular interaction and intramolecular charge transfer effect of the di‐fluorinated end groups with the selenide backbone, PYSe2F‐T exhibits a stronger crystallinity and a more bathochromic absorption to 1000 nm. When blended with the donor, PM6, the PY2SeF‐T‐based all‐PSC demonstrates a higher efficiency of 16.73% with a remarkable short‐circuit current (JSC) of 27.7 mA cm−2, which is the highest JSC for all‐PSCs. Based on these, the ST device based on PM6:PYSe2F‐T demonstrates a superior efficiency of 12.52% with an average visible transmittance of 26.2% and a light utilization efficiency of 3.28%, outperforming the mono‐fluorinated counterpart. The work provides an in‐depth understanding of the above synergistic effects to develop NIR polymer acceptors and establishes a solid foundation for future investigations into large‐area and flexible ST all‐PSCs. [ABSTRACT FROM AUTHOR]

Flexible optoelectronics is the need of the hour as the market moves toward wearable and conformable devices. Crystalline π‐conjugated materials offer high performance as active materials compared to their amorphous counterpart, but they are typically brittle. This poses a significant challenge that needs to be overcome to unfold their potential in optoelectronic devices. Unveiling the molecular packing topology and identifying interaction descriptors that can accommodate strain offers essential guiding principles for developing conjugated materials as active components in flexible optoelectronics. The molecular packing and interaction topology of eight crystal systems of dicyano‐distyrylbenzene derivatives are investigated. Face‐to‐face π‐stacks in an inclined orientation relative to the bending surface can accommodate expansion and compression with minimal molecular motion from their equilibrium positions. This configuration exhibits good compliance towards mechanical strain, while a similar structure with a criss‐cross arrangement capable of distributing applied strain equally in opposite directions enhances the flexibility. Molecular arrangements that cannot reversibly undergo expansion and compression exhibit brittleness. In the isometric CT crystals, the disproportionate strength of the interactions along the bending plane and orthogonal directions makes these materials sustain a moderate bending strain. These results provide an updated explanation for the elastic bending in semiconducting π‐conjugated crystals. [ABSTRACT FROM AUTHOR]

Developing potential hole transport materials (HTMs) is an effective approach to reduce carrier nonradiative recombination and improve the efficiency of perovskite solar cells (PSCs). To investigate the intermolecular and interfacial interactions of HTMs in PSC devices, two molecules (RQ7 and RQ8) with substituent group functionalization are designed by isomerizing ‐F and ‐SMe in the para‐ and ortho‐positions on the side chain of carbazole diphenylamine‐based HTMs. Theoretical simulations indicate that the functionalization of substituent groups in HTMs alters their dipole moments and electronic structures, as well as their intermolecular interactions, hole transport capabilities, and interfacial interactions at the HTMs/perovskite interface. Experimental results show that RQ8 exhibited higher hole mobility, better film‐forming ability, and reduced electron‐hole recombination, resulting in RQ8‐based PSC devices achieving a higher power conversion efficiency than those based on RQ7. Herein, it is demonstrated that isomerous functionalization of substituent groups in carbazole diphenylamine‐based HTMs is a feasible strategy for controlling and regulating the intermolecular and interfacial interactions of HTMs in PSC applications. [ABSTRACT FROM AUTHOR]

An automated pipeline for comprehensive calculation of intermolecular interaction energies based on molecular force-fields using the Tinker molecular modelling package is presented. Starting with non-optimized chemically intuitive monomer structures, the pipeline allows the approximation of global minimum energy monomers and dimers, configuration sampling for various monomer–monomer distances, estimation of coordination numbers by molecular dynamics simulations, and the evaluation of differential pair interaction energies. The latter are used to derive Flory–Huggins parameters and isotropic particle–particle repulsions for Dissipative Particle Dynamics (DPD). The computational results for force fields MM3, MMFF94, OPLS-AA and AMOEBA09 are analyzed with Density Functional Theory (DFT) calculations and DPD simulations for a mixture of the non-ionic polyoxyethylene alkyl ether surfactant C10E4 with water to demonstrate the usefulness of the approach. Scientific Contribution To our knowledge, there is currently no open computational pipeline for differential pair interaction energies at all. This work aims to contribute an (at least academically available, open) approach based on molecular force fields that provides a robust and efficient computational scheme for their automated calculation for small to medium-sized (organic) molecular dimers. The usefulness of the proposed new calculation scheme is demonstrated for the generation of mesoscopic particles with their mutual repulsive interactions. [ABSTRACT FROM AUTHOR]

Thermoplastic polyimides (TPIs) have melt‐processability and adhesive ability, besides the intrinsic advantages of polyimides. To meet the requirements of applications in high‐frequency communication, TPIs with low dielectric constant (Dk)/dielectric loss factor (Df) at high frequency are also desirable. Enhancing the rigidity of polymer chains and simultaneously intermolecular interaction are effective ways to ensure low Dk/Df, which also benefit to heat resistance. However, it is not conducive to thermoplasticity, due to limited movement of polymer chains. To balance the trade‐off between them, we introduce noncoplanar 2,2′‐spirobifluorene groups to modify the rigidity of polymer chains and regulate the twist between electron‐donor moieties (diamine units) and electron‐acceptor moieties (dianhydride units). It leads to rigid polymer chains, which benefits to good heat resistance and dielectric properties. Meanwhile, the resultant irregular chain structure is difficult to crystallize, which results in thermoplasticity. [ABSTRACT FROM AUTHOR]

A series of isostructural reticular frameworks with systematic differences on chemical structures allows us to disclose correlations between specific structural factors and properties, providing insights for designing novel porous materials. However, even slight differences in the molecular structure often lead to non‐isostructural polymorphic frameworks particularly in the case of hydrogen‐bonded organic frameworks (HOFs) because the structures of HOFs are based on a subtle balance of reversible interactions. In this study, we found that three simple analogues of tetracarboxylic acids with naphthalene, quinoxaline, and pyrazinopyrazine cores (NT, QX, and PP, respectively) yielded isostructural solvated HOFs (NT‐1, QX‐1, and PP‐1, respectively), where hydrogen‐bonded sql‐networked sheets were slip‐stacked with closely similar manners. More importantly, these isostructural HOFs underwent structural transformations in different manners upon removal of the guest solvents. Comparison of the crystal structures of the HOFs before and after the transformation revealed that intermolecular interactions of the core significantly affected on rearrangements of hydrogen bonds in the transformation. The results suggest the potential to control the properties and functions of isostructural HOFs by elements in the core. [ABSTRACT FROM AUTHOR]

Heteroleptic silver(I) complexes have recently started to attract attention in thin-film lighting technologies as an alternative to copper(I) analogues due to the lack of flattening distortion upon excitation. However, the interpretation of their photophysical behavior is challenging going from traditional fluorescence/phosphorescence to a temperature-dependent dual emission mechanism and ligand-lock assisted thermally activated delayed fluorescence. Herein, we unveil the photoluminescence behavior of a three-coordinated Ag(I) complex with the N-heterocyclic carbene (NHC) ligand and 2,2′-bipyridine (bpy) as the N^N ligand. In contrast to its low-emissive Cu(I) complex structural analogues, a strong greenish emission was attributed to the presence of aggregates formed by π–π intermolecular interactions as revealed by the X-ray structure and aggregation induced emission (AIE) studies in solution. In addition, the temperature-dependent time-resolved spectroscopic and computational studies demonstrated that the emission mechanism is related to a phosphorescence emission mechanism of two very close lying (ΔE = 0.08 eV) excited triplet states, exhibiting a similar delocalized nature over the bipyridine ligands. Unfortunately, this favourable AIE is lost upon forming homogeneous thin films suitable for lighting devices. Though the films showed very poor emission, the electrochemical stability under device operation conditions is remarkable compared to the prior-art, highlighting the potential of [Ag(NHC)(N^N)][X] complexes in thin-film lighting. [ABSTRACT FROM AUTHOR]

The molecular conformation of giant molecule acceptors (GMAs) plays a significant role in regulating the intermolecular interactions and their photovoltaic performances in organic solar cells (OSCs). For the linear GMA GT‐l, the stronger homo‐molecular interaction causes its aggregation being weakly affected by the donor, thus forming an ordered molecular stacking and proper phase separation in its blend film. The star‐shaped GMA GT‐s‐based blend film shows a dominant hetero‐molecular interaction that suppresses the aggregation of the donor and acceptor, resulting in smaller phase separation and more uniform vertical phase distribution. While for another star‐shaped GMA GTs, the weakest hetero‐molecular interaction causes its blend film to form larger phase separation. Therefore, the GT‐l based OSC with PM6 as donor shows the highest charge mobilities, the fastest charge transfer (CT) process, reduced energy loss and less charge recombination, contributing to a higher power conversion efficiency (PCE) of 19.03%. Comparatively, the PCEs of the OSCs based on GTs and GT‐s are 18.05% and 17.58% respectively. Notably, all the three GMAs based OSCs show excellent thermal stability and long‐term storage stability. This study provides a facile strategy by tuning the linking unit and its connecting mode for designing highly efficient and stable organic photovoltaic materials. [ABSTRACT FROM AUTHOR]

The performance of the recently suggested projected atomic orbitals (PAO) approach as the virtual space in excited state projection-based embedding applications is analysed. The role of the parameters in the PAO generation is discussed and the impact of different choices is evaluated on the ground state of the stacked formaldehyde and pyrrole dimers. A comparison of excitation energies obtained with PAOs and localised virtual orbitals is given and the role of diffuse basis functions is discussed using a benchmark set from previous studies. [ABSTRACT FROM AUTHOR]

This study investigates the potential use of phosphomolybdic acid (POM) as an adsorbate for hazardous organic gases (CH3X, where X = F, Cl, and Br). Density functional theory (DFT) is employed to analyze the interaction between POM and the gases. Structural optimization using the TPSSh/Lanl2Dz level of theory is performed to determine the stable configurations. The adsorption energy of CH3X on POM is calculated to understand the adsorption capabilities and identify the most favorable complex. The results show that CH3F/POM has two optimal adsorption sites, while CH3Br/POM has a larger bond distance and stronger adsorption energy. CH3Cl/POM exhibits three bonding sites. The HOMO-LUMO energy difference decreases after binding, indicating improved conductivity. QTAIM, bond order, and NCI analysis reveal the inter- and intramolecular interactions and bond characteristics. Overall, POM is found to be suitable for adsorbing these gases, especially CH3Br. [ABSTRACT FROM AUTHOR]

Catalyst samples were synthesized by the method of impregnation on the basis of NaX zeolite and Ni metal and their activity was studied in the oxidation process of n-propanol in the temperature range of 423-723K. It has been established that the conversion rate of alcohol and the yield of reaction products on the modified samples increase significantly compared to the original NaX sample. According to the results of the research, it was found that if the reactions of intramolecular and intermolecular dehydration of alcohol predominate at relatively low temperatures, then the reactions of its partial and complete oxidation are accelerated at high temperatures. It was determined that the method of modifying the original NaX zeolite makes it possible to optimize the phase composition of the synthesized catalyst and the size of the active component, which allows to adjust the yield of the main reaction products and reduce the temperature limit of the reaction. As a result of the study, it was found that the average size of NiO particles included in the structure of NaX zeolite is 28314 nm. This suggests that the size of NiO particles in the zeolite structure is at the nanoparticle level. [ABSTRACT FROM AUTHOR]

Context: In this study, we detail the synthesis and crystallographic characterization of an unprecedented structure, specifically hypoxanthinium chloride monohydrate ((I) hereafter), which crystallizes in the monoclinic P21/c space group. A comparative analysis was conducted with four related hypoxanthinium salts: hypoxanthinium bromide monohydrate (II), 9-methylhypoxanthinium chloride monohydrate (III), hypoxanthinium nitrate monohydrate (IV), and hypoxanthinium perchlorate monohydrate (V). This analysis has focused mainly on their crystal packing, hydrogen-bonding networks, and non-classical intermolecular interactions, as elucidated by comprehensive Hirshfeld surface and topological analyses. Theoretical investigation of the nonlinear optical (NLO) properties of the hypoxanthinium derivatives (I–V) was performed using the Density Functional Theory (DFT). Methods: The crystalline environment was simulated using the iterative Supermolecule method (SM), and the static and dynamics linear refractive index, linear polarizability, second-order hyperpolarizability, and the third-order nonlinear susceptibility at the DFT/CAM-B3LYP/6–311++G(d,p) level were computed. The results for the macroscopic third-order nonlinear susceptibility of (II) was found to equal χ 3 = 0.81 × 10 - 20 m 2 / V 2 . By replacing the bromine atom in (II) with a chlorine atom as in (III), the χ 3 value will be multiplied by 2.16, and therefore these results are large enough to suggest the potential application of these crystals as NLO materials. [ABSTRACT FROM AUTHOR]