ArtikelDewetting Behavior of Random Copolymer Films Induced by Solvent Vapor Annealingvon Wang Zhang et al. · 14.03.2023 The dewetting behavior of random copolymer films induced by solvent vapor annealing is reported. Upon annealing of acetone vapor, the poly(styrene-co-acrylonitrile) (SAN) films first present holes and then rupture into droplets which fuse and break ...
ArtikelTheoretical Simulations of Kinetic Isotope Effects on Decarboxylation of 3‐Carboxybenzisoxazolevon Yuqing Xu et al. · 14.03.2023 Kinetic isotope effect values on the decarboxylation of 3-carboxybenzisoxazole have been computed using the second-order Kleinert's variational perturbation theory in the framework of Feynman's path integrals. Compared with the experimental measurem...
ArtikelSize Effects in Gas‐phase C−H Activationvon Bowei Yuan et al. · 14.03.2023 The size effect of the catalyst center plays an essential role in tuning the reactivity and selectivity during gas-phase C−H activation. In this Concept, the authors review the size effects related to early-transition-metal-oxide- and main-group-met...
ArtikelStructure‐Reactivity Insights on the Alkaline Hydrolysis of Organophosphates: Non‐Leaving and Leaving Group Effects in a Bilinear Brønsted‐Like Relationshipvon Valmir B. et al. · 14.03.2023 A bilinear relationship correlating the reactivity of organophosphates towards alkaline hydrolysis with characteristics of the non-leaving and leaving groups is successfully fitted with over 50 reactions. Both non-leaving and leaving group affect th...
ArtikelConcentration Effect, Structural Properties, and Driving Force on Aβ28 Dimerization with and without Zn2+ Cooperation: Learning from Replica Exchange Sampling von Yue Sun et al. · 14.03.2023 Impact on dimerization: Structural features and driving force features for Aβ28 dimerization with and without Zn2+ cooperation. Abstract Zn2+ is a very important factor in promoting the formation of amyloid beta (Aβ) aggregates and amyloid plaques...
ArtikelComposite Mesoporous Silica Nanoparticles with Dual‐color Afterglow for Cross‐correlation‐based Living Cell Imagingvon Mingqi Sun et al. · 14.03.2023 Composite nanoparticle with inherent phosphorescence and delayed fluorescence emission features is developed. Its unique ability in identifying false positive originating from interfering intracellular autofluorescence in live cell fluorescence imag...
ArtikelComputational Studies on the Reactivity of Polycyclic Aromatic Hydrocarbonsvon Yingwei Su et al. · 14.03.2023 Predicting reaction pathways: Wavefunction analysis and transition state theory are powerful approaches for predicting the active reaction sites and reaction pathways of polycyclic aromatic hydrocarbon in both gas and particle phases. Abstract Pol...
ArtikelInfrared Spectroscopy Evidence of Weak Interactions in Frustrated Lewis Pairs Formed by Tris(pentafluorophenyl)boranevon Leandro Ramos et al. · 14.03.2023 Two well-known frustrated Lewis pairs (FLPs) and a classical Lewis adduct (CLP) were studied by infrared spectroscopy aiming to probe intermolecular interactions that sustain the formation of the FLPs. The infrared bands associated with F−C bonds in...
ArtikelEquiatomic binary phases of Copper‐Rare Earth Elements. An overview of monocuprides from first‐principles calculationsvon Riccarda Caputo et al. · 14.03.2023 Equiatomic binary monocuprides of rare earth elements (RECu) mainly show an orthorhombic stable modification in the light rare-earth (RE) region and a cubic one in the heavy RE region. Abstract Equiatomic binary phases of copper with rare earth (R...
ArtikelExciton Nature of Plasma Phase Transition in Warm Dense Fluid Hydrogen: ROKS Simulation von Ilya D. et al. · 14.03.2023 A new mechanism of plasma phase transition in warm dense fluid H2 has been proposed based on analysis of the formation and dissociation of localized excitons during heating. Comparison with experimental data is based on the DFT calculations within t...
ArtikelEfficient Interrogation of the Kinetic Barriers Demarcating Catalytic States of a Tyrosine Kinase with Optimal Physical Descriptors and Mixture Modelsvon Pallab Dutta et al. · 14.03.2023 Efficiently quantifying kinetic barriers: Estimation of activation energies related to rare catalytic activity transitions of Tyrosine Kinases is challenged by high computational expense and obscurity of optimal system descriptors. Here, an upgraded...
ArtikelEthanol Oxidation Reaction Mechanism on Gold Nanowires from Density Functional Theoryvon O. V. et al. · 14.03.2023 Oxidation reaction of ethanol stimulated by Au nanowires (Au−NW) is reported. Using density functional calculations, two NWs are studied, one with a linear atomic chain (LAC) of four Au atoms and another one with an oxygen impurity inserted in the L...
ArtikelSelf‐Organization of Lipid‐Porphyrin Conjugates at the Air/Water Interfacevon Paul Cressey et al. · 14.03.2023 The impact of the lipid backbone structure on the interfacial behavior of lipid-porphyrin conjugates (PyroLSM and PyroLPC) monolayers has been investigated. By combining Langmuir balance to a variety of other physical techniques, we could demonstrat...
ArtikelIn Silico Partial N2 to NH3 Conversion with a Light Atom Moleculevon Stefan Mebs · 14.03.2023 The N≡N triple bond can be cleaved and partially converted to NH3 with the tripodal light atom molecule R3SiH (R=2-dimethylphosphino-6-difluoroborano-phenyl). The N−N bond distance is increased from 1.09 Å in N2 gas to 1.43 Å in the N2-adduct, and s...
ArtikelGalvanostatic Fast Charging of Alkali‐Ion Battery Materials at the Single‐Particle Level: A Map‐Driven Diagnosisvon E. Maximiliano et al. · 14.03.2023 A model to rapidly estimate the specific capacity of single particles of alkali-ion materials under galvanostatic charging/discharging conditions is presented for different C-rates and particle sizes. The capacity is assessed in terms of two scaled ...
ArtikelTriel Bonds with Au Atoms as Electron Donorsvon Zhihao Niu et al. · 14.03.2023 A triel bond is formed for BX3 (X=H, F, Cl, Br, I) and C5H5B, in which the Au atom of AuR2 (R=Cl and CH3) acts as the electron donor. This B⋅⋅⋅Au triel bond is also formed between the positively charged Au atom of AuCl2 and the holes of BX3 and C5H5...
ArtikelHighly Ordered and Thermally Stable FeRh Cluster Superlattice on Graphene for Low‐Temperature Catalytic CO Oxidationvon Hao Yin et al. · 14.03.2023 UHV-STM and pulsed catalytic measurements reveal that Fe−Rh interfaces can facilitate CO oxidation with H2 existence at low temperature on close-packed bimetallic clusters on graphene/Ir. Hydroxyl species on the surface mediate the co-adsorption beh...
ArtikelMagnetic Field‐Enhanced Electrocatalytic Oxygen Evolution on a Mixed‐Valent Cobalt‐Modulated LaCoO3 Catalystvon Ting Wang et al. · 14.03.2023 A novel “mixed-valent cobalt modulation” strategy is presented to enhance the electrocatalytic oxygen evolution reaction (OER) performance of perovskite LaCoO3 (LCO). An optimized catalyst with 1.98 % Co2+/Co3+ exhibits a significant magnetic-field ...
ArtikelIntrinsically Chiral Twist‐Bend Nematogens: Interplay of Molecular and Structural Chirality in the NTB Phasevon Rebecca Walker et al. · 14.03.2023 Relationships between intrinsic and structural chirality in dimeric liquid crystals are explored using new lactate-based chiral compounds exhibiting the rarely-observed chiral N*TB phase. Comparisons of enantiomeric and racemic nonsymmetric dimer pa...
ArtikelUnderstanding the Reactivity of Supported Late Transition Metals on a Bare Anatase (101) Surface: A Periodic Conceptual DFT Investigationvon Xavier Deraet et al. · 14.03.2023 A CDFT prophecy. Periodic conceptual DFT reactivity indices are computed for a variety of single anatase-supported late transition metal atoms and included into a statistically relevant model predicting the strength of the interaction between these ...
ArtikelFront Cover: Intrinsically Chiral Twist‐Bend Nematogens: Interplay of Molecular and Structural Chirality in the NTB Phase (ChemPhysChem 6/2023)von Rebecca Walker et al. · 14.03.2023 The Front Cover is a cartoon depiction of the formation of the heliconical chiral twist-bend nematic phase (N*TB) from its constituent bent molecules. The presence of a single enantiomer of the chiral, lactate-based liquid crystal dimers biases the ...
ArtikelCover Feature: Highly Ordered and Thermally Stable FeRh Cluster Superlattice on Graphene for Low‐Temperature Catalytic CO Oxidation (ChemPhysChem 6/2023)von Hao Yin et al. · 14.03.2023 The Cover Feature shows a three-dimensional rendering of an STM constant current image of Fe clusters self-assembled onto a graphene layer grown with CVD onto an Ir(111) surface. The clusters are an efficient catalyst for the CO-oxidation reaction. ...
ArtikelCover Feature: In Silico Partial N2 to NH3 Conversion with a Light Atom Molecule (ChemPhysChem 6/2023)von Stefan Mebs · 14.03.2023 The Cover Feature represents the concept of employing two (frustrated) Lewis acid-base pairs within a pincer-type compound to activate the defiant N2-molecule; the N≡N triple bond is thereby extended by remarkable 0.34 Å. Once caught by the tailor-m...
ArtikelCover Feature: Galvanostatic Fast Charging of Alkali‐Ion Battery Materials at the Single‐Particle Level: A Map‐Driven Diagnosis (ChemPhysChem 6/2023)von E. Maximiliano et al. · 14.03.2023 The Cover Feature represents a 3-D plot of the loading status of a battery particle material as a function of two galvanostatic dimensionless parameters l and Ξ that depend on the physical properties of the material (particle size d, diffusion coeff...
ArtikelPhotoresponsive Carbon‐Azobenzene Hybrids: A Promising Material for Energy Devicesvon Anjana Baby et al. · 14.03.2023 Azobenzene is an efficient photo-isomerizable compound for solar thermal fuels. In this review, the recent advancements in azobenzene molecules and carbon templates for energy storage devices are discussed. Abstract Advancements in renewable energ...
ArtikelCan Li Atoms Anchored on Boron and Nitrogen Doped Graphene Catalyze Dinitrogen Molecule to Ammonia? A DFT Studyvon Tushar et al. · 29.03.2023Most successful electrochemical conversion of ammonia from dinitrogen molecule reported to date is Li mediated mechanism. In the framework of the above fact and that Li anchored graphene is an experimentally feasible system, the present work is a com...
ArtikelQuantum Chemical Study of the Pressure‐dependent Phosphorescence of [Cr(ddpd)2]3+ in the Solid Statevon Christoph Förster et al. · 29.03.2023The chromium(III) complex [Cr(ddpd)2][BF4]3 shows two spin-flip emission bands in the near-infrared spectral region. These bands shift bathochromically by –14.1 and –7.7 cm–1 kbar–1 under hydrostatic pressure (Angew. Chem. Int. Ed.2018, 57, 11069). T...
ArtikelEffect of Fluorine Substitution on Absorption and Emission Properties of Figure‐eight‐shaped [5]Helicene Dimer : A Computational Study at RI‐MP2/RI‐ADC(2) Levelvon Abhishek Saharia et al. · 29.03.2023Chirality is a very important characteristic of optically active molecules and polyaromatics with helical structures, and plays a vital role in various applications in material science. In the present work, we show the effects of fluorine substitutio...
ArtikelTransitions of Collective Motions Driven by Phase Resettingvon Rui Teng et al. · 29.03.2023Abrupt (i.e. step) environmental changes, such as natural disasters or the intervention of predators, can alter the internal dynamics of groups with active units, leading to the rapid destruction and/or restructuring of the group, with the emergence ...
ArtikelAcetylene‐Mediated Borophosphene Dirac Materials as Efficient Anode Materials for Lithium‐Ion Batteriesvon Karthikraja Esackraj et al. · 28.03.2023 The acy-BP nanosheets are structurally stable and coupled with anisotropic mechanical properties and Dirac electronic properties. They are potential candidates for Li-ion battery anodes with optimal binding energies, diffusion barriers and open circ...
ArtikelPhotocatalytic Hydrogen Production Activity and Mechanism of New Nickel‐Based Sulfur Complexes in Aqueous Solutionvon Haixia Shi et al. · 28.03.2023 Three new nickel catalysts are designed and synthesized, and their photocatalytic hydrogen production performances in aqueous solution are elucidated. The hydrogen production mechanism is discussed by experimental and theoretical methods. Abstract...
ArtikelTheoretical and Experimental Determination of Thermomechanical Properties of Epoxy‐SiO2 Nanocompositesvon Mohammed Mostafa et al. · 28.03.2023 Thermal and mechanical behaviour of epoxy-SiO2 nanocomposites is investigated theoretically using two different representations of the SiO2. Experimental measurements verified the applicability of both models. The calculated radial distribution func...
ArtikelA Toolbox For Glutamine Use In Dissolution Dynamic Nuclear Polarization: From Enzymatic Reaction Monitoring To The Study Of Cellular Metabolic Pathways And Imaging.von Karen Dos et al. · 28.03.2023Glutamine is under scrutiny regarding its metabolic deregulation linked to energetic reprogramming in cancer cells. Many analytical techniques have been used to understand better the impact of the metabolism of amino acids on biological processes, ho...
ArtikelHighly Efficient and Chemoselective Tandem Hydroformylation‐Hydrogenation of Alkenes to Alcohols over g‐CN Supported Bimetallic Rh and Co Nanoparticles Catalystsvon Yu-Kun Shi et al. · 27.03.2023The tandem hydroformylation-hydrogenation of alkenes to corresponding alcohol is a one-pot two-step reaction. The objective of the present work was to design an efficient and stable heterogeneous catalyst for this transformation. To this end, a serie...
ArtikelComprehensive Mechanism for CO Electroreduction on Dual‐Atom‐Catalyst‐Anchored N‐Doped Graphenevon Di Liu et al. · 24.03.2023 A systematic study on e-CORR reaction pathways and C−C coupling with and without explicit solvent models shows that DAC−Cu and DAC−Co can generate C2 products. The preferred C2 product on DAC−Co is ethylene, while the preferred C2 products on DAC−Cu...
ArtikelImpact of Chemical and Physical Properties of Organic Solvents on the Gas and Hydrogen Formation during Laser Synthesis of Gold Nanoparticlesvon Theo Fromme et al. · 24.03.2023 Laser ablation in organic solvents is reported in literature to functionalize laser-generated nanoparticles with carbon shells. In this study, laser ablation of gold was performed in a systematic series of organic solvents to quantify the formed gas...
ArtikelLarge Thermally Irreversible Photoinduced Shift of Selective Light Reflection in Hydrazone‐Containing Cholesteric Polymer Systemsvon Artem Boychuk et al. · 24.03.2023 Cholesteric liquid crystalline hydrazone–containing copolyacrylate and related mixture were synthesized and prepared; their photooptical properties were studied. Photoreversible large shift of the selective light reflection peak was demonstrated und...
ArtikelElucidating the N−N and C−N Bond‐breaking Mechanism in the Photoinduced Formation of Nitrile Iminevon Cristian Guerra et al. · 24.03.2023 The analysis of the correlated electron localization function shows that nitrile imine (photoproduct) forms due to both heterolytic (C−N) and homolytic (N−N) scissions, which are the key bonding events along the reaction coordinate. Abstract In th...
ArtikelReversible Entropy‐Driven Defect Migration and Insulator‐Metal Transition Suppression in VO2 Nanostructures for Phase‐Change Electronic Switchingvon Rui Zhang et al. · 24.03.2023 Surfaces and insulator-metal transition (IMT) are essential but challenging in IMT-triggered electronic switches and optical modulators. Reversible IMT suppression in vanadium dioxide electronic switching are achieved and controlled by reversible en...
ArtikelHeteronuclear Trimetallic MFe2 and M2Fe (M = V, Nb, and Ta) Clusters for Dinitrogen Activationvon Ya-Ya Wang et al. · 23.03.2023Catalysts with heteronuclear metal active sites may have high performance in the nitrogen reduction reaction (NRR), and the in-depth understanding of the reaction mechanisms is crucial for the design of related catalysts. In this work, the dissociati...
ArtikelObservation of a Long‐lived Electronic Coherence Modulated by Vibrational Dynamics in Molecular Nd3+ Complexes at Room Temperaturevon Jayanta Ghosh et al. · 23.03.2023Temporally delayed, phase-locked coherent pairs of near IR femtosecond laser pulses were employed to study electronic coherences in molecular Nd3+ complexes at room temperature. Dissolved and solid complexes were studied under a confocal microscope s...
ArtikelDiffusion Measurements To Understand Dynamics and Structuring in Solutions Involving a Homologous Series of Ionic Liquidsvon Daniel C. et al. · 23.03.2023 Self-assembly and organization in solution are demonstrated to be critical in understanding dif- fusion in mixtures containing an ionic liquid. A key discontinu- ity is seen on increasing the car- bon chain length from hexyl to octyl, consistent wit...
ArtikelA Photoswitchable Solvatochromic Dye for Probing Membrane Ordering by RESOLFT Super‐resolution Microscopyvon Andrew et al. · 22.03.2023A switchable solvatochromic fluorescent dyad can be used to map ordering of lipids in vesicle membranes at a resolution better than the diffraction limit. Combining a Nile Red fluorophore with a photochromic spironaphthoxazine quencher allows the flu...
ArtikelDynamics of Electronically Excited Metal Atoms (Zn and Cd) in Rare Gas Matrices: Simulation of Multiple‐band Emission Using Molecular Dynamics with Quantum Transitionsvon Miguel Lara-Moreno et al. · 21.03.2023A Molecular Dynamics with Quantum Transitions approach is employed to simulate the spectroscopic characteristics of the 1P1↔1S0 transitions of atomic zinc and cadmium in order to gain insight into the excited state behavior of these atoms isolated in...
ArtikelThe Ability of CO2 Capture on Transition Metal‐modified 1T′‐MoS2 Monolayers Controlled by Electric Fieldvon Tianyue Tong et al. · 21.03.2023Herein, we evaluate the CO2 capture ability on the transition metal-modified 1T′-MoS2 monolayers (TM@1T′-MoS2, TM represents a transition metal atom from 3d to 4d except Y, Tc and Cd) under different external electric fields via first-principles calc...
ArtikelPredicting 195Pt NMR Chemical Shifts in Water‐Soluble Inorganic/Organometallic Complexes with a Fast and Simple Protocol Combining Semiempirical Modeling and Machine Learningvon Evgeniia E. et al. · 20.03.2023 A new workflow for the prediction of 195Pt chemical shifts in Pt complexes based on the GFN2-xTB semiempirical method and a machine learning model is presented. Abstract Water-soluble Pt complexes are the key components in medicinal chemistry and ...
ArtikelVibrationally Resolved Inner‐Shell Photoexcitation of the Molecular Anion C2−von S. Schippers et al. · 17.03.2023 Strong contraction: The C2 − molecular anion shrinks when it absorbs an X-ray photon. Abstract Carbon 1s core-hole excitation of the molecular anion C2 − has been experimentally studied at high resolution by employing the photon-ion merged-beams t...
ArtikelNucleus Independent Chemical Shift (NICS) at Small Distances from the Molecular Plane: The Effect of Electron Densityvon Amnon Stanger · 17.03.2023 A 2D nucleus independent chemical shift (NICS) grid and electron density study shows that NICSπ,zz at close proximity to the molecule is influenced by non-aromatic effects. Abstract When close to the molecular plane, the behavior of nucleus indepe...
ArtikelHow Doping Affects the Activity of the Aluminum Oxide Supportvon Linghui Yan et al. · 17.03.2023 Doping may affect both how the H3C−H bond is broken and where is the destiny of the so-formed methyl group. Abstract The performance of heteronuclear clusters [AlXO3]+ (X=Al, AlO4, AlMg2O2, AlZnO, AlAu2, Mg, Y, VO, NbO, TaO) in activating methane ...
ArtikelThe solute polarization and structural effects on the nonlinear optical response of based chromone moleculesvon Neidy et al. · 16.03.2023The solute polarization due to solvent is a an electrostatic quantum effect that impacts diverse molecular properties, including the nonlinear optical response of a material. An iterative procedure that allows updating the solute charge distribution ...
ArtikelSolvent Dependence on Cooperative Vibrational Strong Coupling and Cavity Catalysis von Jaibir Singh et al. · 16.03.2023 Cavity Catalysis: We test the idea of cooperative vibrational strong coupling (VSC) to catalyze an ester hydrolysis process using a combination of esters and solvent system. Selective strong coupling of carbonyl band to an optical cavity mode enhanc...
ArtikelCombined modelling of triply paired coupled electronic states of HO + ion with 3A′′ 2 symmetry using newly developed coupled Eigen modelvon F George · 15.03.2023The multi state triply paired coupled adiabatic electronic states of $X\,^3A^{\prime\prime}, 1\,^3A^{\prime\prime},2\,^3A^{\prime\prime}$ symmetries for the title ion have been modelled using the triply paired coupled eigen valued functions with th...
ArtikelEffects of Edge Functionalization of Nanographenes with Small Aromatic Systemsvon Shusaku Takahashi et al. · 15.03.2023Regulation of the physical properties of nanographenes (NGs) by edge functionalization is an active research area. We conducted a computational study of the effects of edge functionalization on the physical properties of NGs. The computed NGs were mo...
ArtikelInfluence of Thiophene Ring on Molecular Order of Structurally Simple π–Conjugated Smectogens: 13C NMR Studyvon Bathini Veeraprakash et al. · 14.03.2023Structurally simple rod-like π–conjugated mesogens with thiophene directly connected to phenyl, biphenyl, and fluorenone rings with terminal chains are synthesized respectively. The occurrence of smectic A/smectic C phases is concurred by a hot-stag...
ArtikelIndirect Nuclear Spin‐Spin Exchange Coupling through Solvated Electron in Small Sizes of Cyclic and Cage‐shaped Perfluoroalkanesvon Xiao Chen et al. · 14.03.2023Small cyclic (c-CnF2n) and cage-shaped (CnFn) perfluoroalkanes are better electron scavengers, and can form solvated electron (e−sol) systems (e@c-CnF2n and e@CnFn). There are many studies on structures and properties of these e−sol systems, but how...
ArtikelRationalizing Aggregate Structures with Orbital Contributions to the Exchange‐Repulsion Energy von Johannes Henrichsmeyer et al. · 13.03.2023 Repulsive interactions are shown to have decisive influence on the structure of prototypical systems with noncovalent interactions. We provide a pictorial molecular orbital based model of the exchange-repulsion that rationalizes previously poorly un...
ArtikelCO2 Reduction Mechanism on the Cu2O(110) Surface: A First‐Principles Studyvon Haihang Chen et al. · 13.03.2023 The ideal Cu2O(110) surface is the most active and selective for CO2 reduction to methanol. The Cu(0) at O vacancy and Cu/Cu2O interface promotes the adsorption and activation of CO2, but the removal of residual O becomes potential-limiting. With in...
ArtikelDouble Hook Perylene Diimide as a New Receptor for PAHs: An Experimental and Theoretical Studyvon Nadia et al. · 10.03.2023In a one-step reaction, we prepared a dibenzylamine perylene diimide derivative (PDI). Its double hook structure allows for self-association with a constant of Kd ~108 M-1 determined by fluorescence. We confirmed its ability to bind PAHs using UV/Vis...
ArtikelIs DFT Accurate Enough to Calculate Regioselectivity? The Case of 1,3‐Dipolar Cycloaddition of Azide to Alkynes and Alkenesvon Giorgio Molteni et al. · 10.03.2023The importance of regioselectivity in 1,3-dipolar cycloadditions (DCs) makes it surprising that no benchmarking study on this problem has appeared. We investigated whether DFT calculations are an accurate tool to predict the regioselectivity of uncat...
ArtikelA Computational Study on Closed‐Shell Molecular Hexafluorides MF6 (M=S, Se, Te, Po, Xe, Rn, Cr, Mo, W, U) – Molecular Structure, Anharmonic Frequency Calculations, and Prediction of the NdF6 Moleculevon Tim Graubner et al. · 09.03.2023 The anharmonic IR spectra of known and unknown closed-shell molecular hexafluorides MF6 (with M=Cr, Mo, W, U, S, Se, Te, Po, Xe, Rn) were calculated at the CCSD(T)/cc-pVTZ(-PP) level of theory. The unknown NdF6 molecule was predicted to be stable on...
ArtikelTime‐resolved, Gas‐phase Kinetic and Quantum Chemical Studies of the Reaction of Germylene with Hydrogen Chloridevon Rosa Becerra et al. · 09.03.2023 Kinetic measurements combined with quantum chemical theory show that this fast reaction proceeds solely via this pathway, with no GeH3Cl intermediary. Abstract Time-resolved studies of germylene, GeH2, generated by laser flash photolysis of 3,4-di...
ArtikelConstructing Potential Energy Surface with Correlated Theory for Dipeptides Using Molecular Tailoring Approachvon Subodh S. et al. · 09.03.2023 Employing a fragment-based molecular tailoring approach, the construction of PES of dipeptides using correlated methods with the computational economy is demonstrated. The MP2/aug-cc-pVTZ and CCSD/aug-cc-pVDZ level PES are constructed for prototype ...
ArtikelHow Different are the Diamagnetic and Paramagnetic Contributions to Off‐Nucleus Shielding in Aromatic and Antiaromatic Rings?von Peter B. · 09.03.2023 Analysis of the diamagnetic and paramagnetic contributions to off-nucleus shielding in benzene and cyclobutadiene shows that the different off-nucleus shielding pictures and nucleus-independent chemical shift (NICS) values for antiaromatic and antia...
ArtikelLigand Effect on Physicochemical Properties of Ionic Liquidvon Alok Rout et al. · 09.03.2023 Altering properties of an IL phase: The Presence of various classes of molecular ligands/extractants effectively alters the physicochemical properties of an IL phase ([C4mim][NTf2]) used as the diluent for the solvent extraction of metal ions depend...
ArtikelNi‐Ti Intercalated and Supported Bentonite for Selective Hydrogenation of Cinnamaldehydevon Yiyuan Xu et al. · 06.03.2023 Ni-Ti intercalated bentonite (Ni-Ti-bentonite) exhibits a better catalytic performance in the chemoselective hydrogenation of cinnamaldehyde (CAL) to hydrocinnamaldehyde (HCAL), which could be attributed to the fact that Ni0 covers the Lewis acid si...
ArtikelRevealing the Chemical State of Palladium in Operating In2O3 Gas Sensors: Metallic Pd Enhances Sensing Response and Intermetallic InxPdy Compound Blocks Itvon Oleksandr Ovsianytskyi et al. · 06.03.2023 The way in which the chemical state of Pd in the PdO/rh-In2O3 system (PdO, Pd, PdHx, and InxPdy) and the system's overall structure correlate with the H2 gas adsorption capability is investigated. The authors apply a combination of operando gas meas...
ArtikelMo Cluster Support on C2N as a Highly‐efficient Catalyst for Electrocatalytic Nitrogen Reduction Reactionvon Yuke Chen et al. · 03.03.2023 Various types of active sites on the surface of Mo12 clusters provide suitable reaction paths for N2 transition and its intermediates to NH3, thereby reduce the energy barrier of electrocatalytic nitrogen reduction reaction. Abstract The conversio...
ArtikelSupercritical CO2‐induced New Chemical Bond of C−O−Si in Graphdiyne to Achieve Robust Room‐Temperature Ferromagnetismvon Jian Yang et al. · 02.03.2023 Room-temperature ferromagnetism is successfully achieved in graphdiyne by supercritical CO2 treatment. Structural defects induced by supercritical CO2 in graphdiyne provides local magnetic moments that lead to ferromagnetism. Furthermore, the format...
ArtikelExploring Glycosylated Soy Isoflavones Affinities toward G‐tetrads as Studied by Survival Yield Methodvon Olga Stężycka et al. · 02.03.2023 Isoflavone glucosides in soy-based food supplements form adducts with guanosine tetrads and deoxyguanosine tetrads (G-tetrads). The adducts are analyzed by using electrospray ionization-collision induced dissociation-mass spectrometry and survival y...
ArtikelTheoretical Study of the Hydroxyl‐Radical‐Initiated Degradation Mechanism, Kinetics, and Subsequent Evolution of Methyl and Ethyl Iodides in the Atmospherevon Xiang‐Huan Liu et al. · 28.02.2023 The atmospheric transformation mechanisms and degradation kinetic properties of CH3I and CH3CH2I, mediated by the ⋅OH radical, are investigated using MP2 and CCSD(T) methods. Abstract The degradation and transformation of iodinated alkanes are cru...
ArtikelGeneration of Helical States ‐ Breaking of Symmetries, Curie’s Principle, and Excited Statesvon J. Sabalot-Cuzzubbo et al. · 28.02.2023Herein, we deeply detail for the very first time mathematical con- cepts behind the generation of helical molecular orbitals (MOs) for linear chains of atoms. We first give a definition of helical MOs and we provide an index measuring how far a given...
ArtikelStatistical Equivalence of Quantum Chemical Methods for Energy Distribution in Water Clustersvon Andrey M. · 28.02.2023 Collective properties of a statistical ensemble of molecules may be invariant to the method employed for their calculation. This hypothesis is validated in hydrogen-bond networks of water clusters. It is demonstrated that the form of the energy dist...
ArtikelPhotoionization Bands of Cyanogen: Multi‐Mode Vibronic Coupling and Renner‐Teller Effectsvon Mamilwar Rani et al. · 27.02.2023Multi-mode vibronic coupling in the X2Πg, A2Σ+g, B2Σ+u and C2Πu electronic states of Cyanogen radical cation (C2N2+) is investigated with the aid of ab initio quantum chemistry and first principles quantum dynamics methods. The electronic degenerate ...
ArtikelA Case Study on the Use of Binding Free Energies to Screen Inhibitors of Human Carbonic Anhydrase IIvon Satyajit Khatua et al. · 24.02.2023 The underlying dynamics of binding and unbinding of a ligand to an enzyme and its interactions with amino acid residues modify the enthalpy, entropy, and total binding free energy estimated using a single molecular dynamics trajectory in combination...
ArtikelCarbon Dioxide Reduction on Transition Metal Dichalcogenides with Ni and Cu Edge Doping: A Density‐Functional Theory Studyvon Ronen Kruchinin et al. · 24.02.2023 Density functional theory study of CO2 reduction to methane over Mo/W-based and S/Se-based Transition-metal dichalcogenides with non-, Ni- and Cu-doping. The results show TMDs based on sulfur with copper doping as efficient candidates forthe catalys...
ArtikelTheoretical Study on Zigzag Boron Nitride Nanowiresvon Feng‐Yin Li et al. · 24.02.2023 One-dimensional boron nitride nanowires composed of B−B and N−N bonds are predicted via density functional calculations. The band gaps vary between 1.8 and 3.5 eV under strains, which covers the entire visible light region. Together with high mechan...
ArtikelInteraction of Cyanoacrylate with Metal Oxide Surfaces (Cu, Al)von Philipp Moritz et al. · 23.02.2023 The molecular interactions at the interface between a cyanoacrylate “superglue” and native oxide metal surfaces are investigated using various spectroscopic methods. A combination of hydrogen bonds and an ionic interaction is identified and a reacti...
ArtikelWeak Interactions Initiate C−H and C−C Bond Dissociation of Ethane on Nbn+ Clustersvon Wen Gan et al. · 23.02.2023 The gas-phase reactivity of Nb n + clusters with acetylene is studied utilizing a customized laminar flow tube reactor in tandem with a customized triple quadrupole mass spectrometer, illustrating how weak interactions initiate the C−H and C−C b...
ArtikelRing‐polymer Molecular Dynamics Simulation for the Adsorption of H2 on Ice Clusters (H2O)n (n=8, 10, and 12)von Tatsuhiro Murakami et al. · 23.02.2023 Hydrogen adsorption and desorption on the water ice clusters (H2O) n (n=8, 10, and 12) are investigated by theoretical approach which is a ring-polymer molecular dynamics method. The temperature-dependent and size-independent features are observ...
ArtikelInsights into Nitrogen‐doped Carbon for Oxygen Reduction: The Role of Graphitic and Pyridinic Nitrogen Speciesvon Dongliang Wang et al. · 22.02.2023 Elucidating the role of nitrogen species for oxygen reduction reaction (ORR) in nitrogen doped carbons (N/Cs) is important to explore high-performance N/C catalysts. Three N/C samples with distinct nitrogen species are synthesized. Experiments and d...
ArtikelElectrostatic Fields Stimulate Absorption of Small Neutral Molecules in Gradient Polyelectrolyte Brushesvon Leon A. et al. · 22.02.2023 Modulating surface absorption with electricity: The absorption properties of a polyelectrolyte brush with an exponential charge-density gradient along the polymer backbones is investigated using coarse-grained molecular dynamics simulations. Applied...
ArtikelAryl Boronic Acids in Columnar Stacked Co‐crystalline Materials: Key‐Factors Governing the Assembly with Quinonesvon Manuel Petroselli et al. · 21.02.2023 Columnarly stacked materials: How do aryl boronic acids and quinones stick together? We report a theoretical study on the key factors governing the assembly between aromatic boronic acids and quinones, highlighting the importance of BO−H conformatio...
ArtikelPotential of AMnO3 (A=Ca, Sr, Ba, La) as Active Layer in Inorganic Perovskite Solar Cellsvon Matko Mužević et al. · 20.02.2023 Potential of AMnO3 perovskites is explored and analysed using density functional theory calculations and supported by experimental measurements. They show absorption coefficients of the order 105 cm−1, which could potentially be used as a stable ino...
ArtikelTuning Molecular Electron Affinities against Atomic Electronegativities by Spatial Expansion of a π‐Systemvon Elena A. et al. · 20.02.2023 Size does matter: Replacing in 2,1,3-benzochalcogenadiazoles C6R4N2E and C6H2R2N2E (E=S, Se, Te; R=H, F, Cl, Br, I) lighter/smaller E and non-hydrogen R atoms with heavier/bigger, i. e., decreasing atomic electronegativities, increases molecular ele...
ArtikelHetero‐Polar Sextuple Bond: A Relativistic Quantum Chemical Study von Amlan J. et al. · 20.02.2023 Relativistic quantum chemical calculations reveal sextuple bond in the singlet ground state of RhSc diatomic species. Abstract Number of bonds formed by sharing an electron pair between two atoms is not restricted to one, it can go beyond four and...
ArtikelCryogenic Chemistry and Quantitative Non‐Thermal Desorption from Pure Methanol Ices: High‐Energy Electron versus X‐Ray Induced Processesvon Daniela Torres‐Díaz et al. · 17.02.2023 High-energy electron irradiation of methanol ices at 23 K leads to non-thermal desorption of both methanol and several neutral products. The gas phase enrichment, measured quantitatively for electrons, confirms the key contribution of the Auger elec...
ArtikelCompetition Between the Two σ‐Holes in the Formation of a Chalcogen Bondvon Steve Scheiner · 17.02.2023 Chalcogen bonds are formed when a region near a chalcogen atom known as a σ-hole acquires a partial positive charge, which can attract a nucleophile. Each such σ-hole lies directly opposite to a substituent bound to the central chalcogen atom, so di...
ArtikelUnderstanding the Target Search by Multiple Transcription Factors on Nucleosomal DNAvon Sujeet Kumar et al. · 16.02.2023 Multiple Transcription Factors (TFs) search on Nucleosome: The target search efficiency for a pair of TFs on nucleosome DNA relies on nucleosome dynamics, protein-protein complex formation rates, their dissociation kinetics and spatial position of t...
ArtikelImproved Performance of All‐Inorganic Perovskite Light‐emitting Diodes via Nanostructured Stamp Imprintingvon Hai‐Jing Zhang et al. · 14.02.2023 A thermal imprinting strategy using nanostructured stamps is utilized to selectively manipulate the nucleation and growth in nanoscale to produce small-sized grain with improved crystal quality and surface morphology of the film. The luminance and e...
ArtikelUsage of the Y‐Rule and the Effect of the Occurrence of Heteroatoms (N, S) on the Frontier Molecular Orbitals Gap of Polycyclic Aromatic Hydrocarbons (PAHs), and Asphaltene‐PAHsvon Yosadara Ruiz‐Morales et al. · 14.02.2023 Heteroatoms in PAHs and in asphaltene-PAHs: A systematic study of the effect of adding N and S atoms to polycyclic aromatic hydrocarbon (PAH) molecules on the frontier molecular orbitals′ (HOMO-LUMO) energy gap and on the π-electronic distribution i...
ArtikelPerfect Core‐Shell Octahedral B@B38+, Be@B38, and Zn@B38 with an Octa‐Coordinate Center as Superatoms Following the Octet Rulevon Qiao‐Qiao Yan et al. · 14.02.2023 Extensive global minimum searches augmented with first-principles theory calculations predict the smallest perfect core-shell octahedral borospherene Oh B@B38 + and its endohedral metallo-borospherene analogs Oh Be@B38 and Oh Zn@B38 which, as sup...
ArtikelAdsorption of Carbamazepine in All‐Silica Zeolites Studied with Density Functional Theory Calculations von Michael Fischer · 10.02.2023 The interaction of carbamazepine with eleven all-silica zeolites is studied using dispersion-corrected density functional theory calculations. The calculations not only allow the prediction of highly promising adsorbents for carbamazepine removal, b...
ArtikelInter‐Alkali‐Metal Dative Bond in the MMN3− (M=Alkali Metal) Clustervon Ankur Kanti · 10.02.2023 Alkalide – alkali metal dative bonding has been proposed in the MMN3 − cluster (M=alkali metal). Abstract Alkali metals are generally Lewis acids. On the contrary, Lewis basic character of alkali metals forming donor – acceptor complexes is a very...
ArtikelComputational Study on Chemoselective Difunctionalization of Unactivated Alkenes with Radical‐mediated Remote Functional Group Migrationvon Ferruh Lafzi et al. · 10.02.2023 The radical-mediated chemoselective difunctionalization of tertiary alcohol substituted aliphatic alkenes is investigated using high-level coupled-cluster methods such as DLPNO-CCSD(T). The computations demonstrate that the formation of the cyclic v...
ArtikelTorsional Rotation in Ditopic Receptor Host and its Complex Formation with Resorcinol Guest: A Computational Studyvon Haobam et al. · 07.02.2023Noncovalent interactions due to the presence of heteroatoms in supramolecular compounds have gained a lot of attention. These different heteroatom-based supramolecular compounds have inspired us to examine the noncovalent interaction in the isolated ...
ArtikelEmpirical Hydrogen Bonding Donor (HBD) Parameters of Organic Solvents Using Solvatochromic Probes – A Critical Evaluationvon Stefan Spange et al. · 06.02.2023 The pK a value of the solvatochromic probe in relation to that of the solvent molecule (pK aS) is decisive for whether acid-base or volumetric effects, with respect to the molar concentration N of the solvent, preferentially determine the empi...
ArtikelInsights into the CO2 Capture Capacity of Covalent Organic Frameworksvon Saurabh V. et al. · 03.02.2023 An inexpensive computational method is developed to unravel the structure-property relationship of complex covalent organic framework (COFs) molecules toward CO2 capture. The model is tested on boronic acid derived COFs. Increasing the number of -NH...
ArtikelCation co‐intercalation in potassium copper(II) hexacyanoferratesvon Antonio Doménech-Carbó et al. · 03.02.2023The cation-insertion solid state electrochemistry of a potassium copper(II) hexacyanoferrate in contact with LiClO4/DMSO, NaPF6/DMSO, and KPF6/DMSO electrolytes has been theoretically and experimentally studied using the voltammetry of immobilized pa...
ArtikelC−H Activation by Iron‐Vanadium Bimetallic Oxide Cluster Anions FeV3O10− and FeV5O15−: A Comparison with Scandium‐Vanadium Oxide Clustersvon Gong‐Ping Wei et al. · 03.02.2023 Hydrogen atom abstraction from C2−C4 alkanes at 298 K by iron-vanadium bimetallic oxide cluster anions FeV3O10 − and FeV5O15 − featuring iron-bonded O⋅− radicals (Fe−O⋅−) is characterized experimentally, which offers a new regulation rule to tune th...
ArtikelThiacalixarene Appended Azo‐based Supramolecular Systems: Self‐assembly and Photo Tuning Reversible Liquid Crystalline Propertiesvon Vipul Desai et al. · 31.01.2023 Reversibly photoswitchable bowl-shaped supramolecular systems for thermally stable columnar phase with self-assembly and reversible liquid crystalline properties are reported. Abstract Four new azo-based supramolecular materials containing thiacal...
ArtikelTunnelling Dynamics of Kicked Systems: A Route to Tunnelling Controlvon Susmita Kar et al. · 30.01.2023 Complete destruction of tunnelling (CDT) can only be achieved with continuous temporal perturbation on symmetric double and triple well model quantum systems. The discontinuous one shows tunnelling without CDT or over-barrier transition, depending o...
ArtikelIntegrating Photoluminescence and Ferromagnetism in Carbon Quantum Dot/ZnO by Interfacial Orbital Hybridization for Multifunctional Bioprobesvon Lifen Wang et al. · 30.01.2023 A feasible atomic-hybridization strategy is proposed to anchor carbon quantum dots onto ZnO microsphere surface via breakage of C=O bonds and subsequent Zn-3d and C-2p orbital hybridization, thus leading to coexistence of photoluminescence and magne...
ArtikelSelf‐organization in an Open Reaction Network for Developing High‐function Organized Molecular Systems von Yoshiharu Mukouyama et al. · 27.01.2023 The steady state of an open reaction network (ORN) characteristically evolves toward a structurally highly ordered and high-efficiency state. Using this property, it is possible to produce high-function organized molecular systems such as an efficie...
ArtikelDFT‐based Machine Learning for Ensemble Effect of Pd@Au Electrocatalysts on CO2 Reduction Reactionvon Fuzhu Liu et al. · 25.01.2023 The ensemble effect on the CO2 reduction reaction for the Pd@Au catalyst surface was investigated by using density functional theory and machine-learning (regression and clustering) methods. The active site-dependent reaction mechanism was found tha...
