Fu Dai,Yixing Zeng,Shaoze Zhang,Yaochun Yao,Dengyang Luo,Rui Yang,Fushuang Zhou,Keyu Zhang,Yin Li,Junxian Hu,Bin Yang,Yan He,Honglai Liu
This study employs first-principles and ab-initio molecular dynamics (AIMD) calculations to investigate the interactions between mixed ionic liquids (ILs) and lithium metal surfaces. The ionic liquids systems investigated consist of two cations, [C 4 mpyr] + and [C 4 mpip] + , paired with five anions: FSI, TFSI, FTFSI, MCTFSI, and OTF. These ILs were arranged in a checkerboard pattern on the lithium surface, and their interfacial interactions were analyzed through independent gradient model (IGM), electron density difference (EDD) and population analysis. The results reveal that introducing the [C 4 mpip] + increases adsorption energies in systems with FSI, FTFSI, and MCTFSI anions, while decreasing it in systems with TFSI and OTF. Additionally, mixed cation and anion systems exhibit lower viscosity and enhanced ionic conductivity due to reduced hydrogen bonding, which contributes to improved performance in lithium batteries. Furthermore, AIMD simulations suggest that the addition of FSI anions accelerates the decomposition of MCTFSI anions. These findings provide valuable insights for designing optimized ionic liquid electrolytes, with potential applications in improving the stability and performance of lithium-metal anodes in future battery technologies.
{"title":"Structure and Interaction of Mixed Ionic Liquids on Lithium from First-Principles","authors":"Fu Dai,Yixing Zeng,Shaoze Zhang,Yaochun Yao,Dengyang Luo,Rui Yang,Fushuang Zhou,Keyu Zhang,Yin Li,Junxian Hu,Bin Yang,Yan He,Honglai Liu","doi":"10.1039/d6cp02281b","DOIUrl":"https://doi.org/10.1039/d6cp02281b","url":null,"abstract":"This study employs first-principles and ab-initio molecular dynamics (AIMD) calculations to investigate the interactions between mixed ionic liquids (ILs) and lithium metal surfaces. The ionic liquids systems investigated consist of two cations, [C 4 mpyr] + and [C 4 mpip] + , paired with five anions: FSI, TFSI, FTFSI, MCTFSI, and OTF. These ILs were arranged in a checkerboard pattern on the lithium surface, and their interfacial interactions were analyzed through independent gradient model (IGM), electron density difference (EDD) and population analysis. The results reveal that introducing the [C 4 mpip] + increases adsorption energies in systems with FSI, FTFSI, and MCTFSI anions, while decreasing it in systems with TFSI and OTF. Additionally, mixed cation and anion systems exhibit lower viscosity and enhanced ionic conductivity due to reduced hydrogen bonding, which contributes to improved performance in lithium batteries. Furthermore, AIMD simulations suggest that the addition of FSI anions accelerates the decomposition of MCTFSI anions. These findings provide valuable insights for designing optimized ionic liquid electrolytes, with potential applications in improving the stability and performance of lithium-metal anodes in future battery technologies.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"24 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225803","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The reaction of ethylene (C2H4) with hydroxyl radical (OH) plays a vital role in both hydrocarbon combustion and atmospheric chemistry. In this theoretical study, this reaction was investigated using the high-accuracy HEAT protocol combined with pragmatic two-dimensional master equation (2DME) analysis and semiclassical transition state theory (SCTST). The calculated HEAT reaction enthalpies show excellent agreement with benchmark ATcT values, falling well within the target uncertainty of 0.2 kcal mol⁻¹. Two primary reaction mechanisms were confirmed: OH-addition and direct H-abstraction. Under ambient atmospheric conditions, OH-addition yielding the thermalized stabilization product HOCH2CH2, is the major pathway, whereas direct H-abstraction dominates at combustion temperatures, with the transition found to occur around 800–850 K. By adjusting the HEAT-calculated energy of the inner transition state for the OH-addition step (TS1) by only -0.32 kcal mol⁻¹, nearly all available experimental datasets for pressure-dependent falloff curves (1 – 1000 Torr) at room temperature, as well the available pressure-dependent (0.01 – 100 atm) rate data as a function of temperature (600 – 2000 K) were successfully reproduced, generally within 20%. Vinyl alcohol produced via an addition/elimination mechanism was characterized under high-temperature flame conditions with an estimated yield of 10 ± 2%, which aligns well with literature values. Finally, production of formaldehyde + CH3 radical and acetaldehyde + H-atom by fast tunneling was identified and quantified for the first time as the principal ― if not only ― pathways at the very low temperatures of the interstellar medium.
{"title":"A High-Level Theoretical Study of the CH + OH Reaction","authors":"Thanh Lam Nguyen,Jozef Peeters","doi":"10.1039/d6cp03577a","DOIUrl":"https://doi.org/10.1039/d6cp03577a","url":null,"abstract":"The reaction of ethylene (C2H4) with hydroxyl radical (OH) plays a vital role in both hydrocarbon combustion and atmospheric chemistry. In this theoretical study, this reaction was investigated using the high-accuracy HEAT protocol combined with pragmatic two-dimensional master equation (2DME) analysis and semiclassical transition state theory (SCTST). The calculated HEAT reaction enthalpies show excellent agreement with benchmark ATcT values, falling well within the target uncertainty of 0.2 kcal mol⁻¹. Two primary reaction mechanisms were confirmed: OH-addition and direct H-abstraction. Under ambient atmospheric conditions, OH-addition yielding the thermalized stabilization product HOCH2CH2, is the major pathway, whereas direct H-abstraction dominates at combustion temperatures, with the transition found to occur around 800–850 K. By adjusting the HEAT-calculated energy of the inner transition state for the OH-addition step (TS1) by only -0.32 kcal mol⁻¹, nearly all available experimental datasets for pressure-dependent falloff curves (1 – 1000 Torr) at room temperature, as well the available pressure-dependent (0.01 – 100 atm) rate data as a function of temperature (600 – 2000 K) were successfully reproduced, generally within 20%. Vinyl alcohol produced via an addition/elimination mechanism was characterized under high-temperature flame conditions with an estimated yield of 10 ± 2%, which aligns well with literature values. Finally, production of formaldehyde + CH3 radical and acetaldehyde + H-atom by fast tunneling was identified and quantified for the first time as the principal ― if not only ― pathways at the very low temperatures of the interstellar medium.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"62 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225836","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rasa Keruckiene, Kaspars Leduskrasts, Ho-Chia Tsai, Mariia Stanitska, Daiana Ospanova, Dmytro Volyniuk, Edgars Suna, Shi-Wei Chu, J V Grazulevicius
Molecular charge modulation offers a promising strategy for controlling the excited-state properties and aggregation behavior of organic luminophores. Nevertheless, the consequences of cationization strongly depend on the molecular structure. Herein, we investigate a twisted π-extended pyridine-dimethylacridan derivative (PyAcr) and its cationic pyridinium analogue (PyAcr+) to elucidate how neutral-to-cationic transformation affects their photophysical properties. Experimental characterization combined with theoretical calculations provides insight into the relationship between molecular structure, charge distribution, excited-state character, and emission behavior. PyAcr exhibits aggregation-induced delayed fluorescence (AIDF), accompanied by a moderate photoluminescence quantum yield of 45% and strong two-photon-excited fluorescence (TPEF) under near-infrared excitation. In contrast, conversion of PyAcr to PyAcr+ alters its aggregation behavior and results in substantially weakened emission, likely reflecting the combined effects of cation formation and the structural modification introduced upon quaternization. Both derivatives exhibit high thermal stability, with onset temperatures of thermal degradation above 360 °C, good electrochemical stability, and small singlet-triplet energy gaps of 0.07-0.13 eV. Overall, the results demonstrate that cationization alone does not necessarily enhance luminescence and that the interplay between molecular charge, electronic coupling, and aggregation is critical for controlling excited-state dynamics. These structure-property relationships provide useful guidelines for the rational design of environment-responsive luminophores, while PyAcr shows promise as a two-photon-excited probe for bioimaging.
{"title":"Aggregation-activated delayed and two-photon fluorescence in a charge-modulated pyridine-acridan luminophore.","authors":"Rasa Keruckiene, Kaspars Leduskrasts, Ho-Chia Tsai, Mariia Stanitska, Daiana Ospanova, Dmytro Volyniuk, Edgars Suna, Shi-Wei Chu, J V Grazulevicius","doi":"10.1039/d6cp02166b","DOIUrl":"https://doi.org/10.1039/d6cp02166b","url":null,"abstract":"<p><p>Molecular charge modulation offers a promising strategy for controlling the excited-state properties and aggregation behavior of organic luminophores. Nevertheless, the consequences of cationization strongly depend on the molecular structure. Herein, we investigate a twisted π-extended pyridine-dimethylacridan derivative (PyAcr) and its cationic pyridinium analogue (PyAcr+) to elucidate how neutral-to-cationic transformation affects their photophysical properties. Experimental characterization combined with theoretical calculations provides insight into the relationship between molecular structure, charge distribution, excited-state character, and emission behavior. PyAcr exhibits aggregation-induced delayed fluorescence (AIDF), accompanied by a moderate photoluminescence quantum yield of 45% and strong two-photon-excited fluorescence (TPEF) under near-infrared excitation. In contrast, conversion of PyAcr to PyAcr+ alters its aggregation behavior and results in substantially weakened emission, likely reflecting the combined effects of cation formation and the structural modification introduced upon quaternization. Both derivatives exhibit high thermal stability, with onset temperatures of thermal degradation above 360 °C, good electrochemical stability, and small singlet-triplet energy gaps of 0.07-0.13 eV. Overall, the results demonstrate that cationization alone does not necessarily enhance luminescence and that the interplay between molecular charge, electronic coupling, and aggregation is critical for controlling excited-state dynamics. These structure-property relationships provide useful guidelines for the rational design of environment-responsive luminophores, while PyAcr shows promise as a two-photon-excited probe for bioimaging.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":3.0,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222849","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Franziska Sabath,Rasmus Väinö Erik Nilsson,Tobias Dickbreder,Georg Stammler,Ralf Bechstein,Angelika Kuhnle,Bernhard Reischl
Cloud properties affecting weather and climate, such as albedo or likelihood to precipitate, strongly depend on whether cloud droplets are liquid or frozen. Heterogeneous ice nucleation in the presence of ice nucleating particles (INP) predominates in ice cloud formation. An important example of INPs are K-feldspar mineral dust particles. The term K-feldspar describes a group of minerals with the same chemical composition (KSi3AlO8), but with differences in crystallographic structure, Si/Al order and (surface) microstructure. K-feldspars with a high Si/Al order (microcline) were found to often have a higher IN efficiency than K-feldspars with a lower Si/Al order (orthoclase and sanidine). However, the origin of this difference in ice nucleation efficiency is not yet clarified. Here, we present an experimental and theoretical comparison between the hydration layer structures of the orthoclase- and microcline-water interfaces. The hydration layer structure strongly affects the heterogeneous ice nucleation mechanism in immersion freezing. The two- and three-dimensional atomic force microscopy experiments and the molecular dynamic simulations at the orthoclase (001)- and (010)-water interface both reveal a similar checkerboard-like structure 0.5 nm above the surfaces with a spacing of (0.27±0.03) nm between the water layers, in good agreement with atomistic simulations. We observe no significant impact of the Si/Al-order on the hydration structures on orthoclase and microcline, but simulations indicate changes in the hydration layer dynamics.
{"title":"Does the Si/Al-order in K-feldspars influence their hydration structure?","authors":"Franziska Sabath,Rasmus Väinö Erik Nilsson,Tobias Dickbreder,Georg Stammler,Ralf Bechstein,Angelika Kuhnle,Bernhard Reischl","doi":"10.1039/d6cp01884j","DOIUrl":"https://doi.org/10.1039/d6cp01884j","url":null,"abstract":"Cloud properties affecting weather and climate, such as albedo or likelihood to precipitate, strongly depend on whether cloud droplets are liquid or frozen. Heterogeneous ice nucleation in the presence of ice nucleating particles (INP) predominates in ice cloud formation. An important example of INPs are K-feldspar mineral dust particles. The term K-feldspar describes a group of minerals with the same chemical composition (KSi3AlO8), but with differences in crystallographic structure, Si/Al order and (surface) microstructure. K-feldspars with a high Si/Al order (microcline) were found to often have a higher IN efficiency than K-feldspars with a lower Si/Al order (orthoclase and sanidine). However, the origin of this difference in ice nucleation efficiency is not yet clarified. Here, we present an experimental and theoretical comparison between the hydration layer structures of the orthoclase- and microcline-water interfaces. The hydration layer structure strongly affects the heterogeneous ice nucleation mechanism in immersion freezing. The two- and three-dimensional atomic force microscopy experiments and the molecular dynamic simulations at the orthoclase (001)- and (010)-water interface both reveal a similar checkerboard-like structure 0.5 nm above the surfaces with a spacing of (0.27±0.03) nm between the water layers, in good agreement with atomistic simulations. We observe no significant impact of the Si/Al-order on the hydration structures on orthoclase and microcline, but simulations indicate changes in the hydration layer dynamics.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"28 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Understanding how electronic structure regulates N2 adsorption geometry is crucial for establishing structure-activity relationships in the nitrogen reduction reaction (NRR), yet the intrinsic relationship between electronic structure modulation and adsorption geometry remains poorly understood. Herein, density functional theory calculations are employed to investigate NRR on graphdiyne-supported Mo-TM dual-atom catalysts (Mo-TM@GDY, TM = 3d, 4d, and 5d transition metals). We demonstrate that the electronic structure of the secondary metal center drives a continuous transition of N2 adsorption geometry from side-on to end-on configurations across the Mo-TM@GDY series, accompanied by charge transfer to adsorbed N2 ranging from 0.19 to 0.97 e. This adsorption geometry transition governs N2 activation and reaction energetics, leading to distinct NRR pathways in which side-on adsorption promotes synergistic dual-metal activation of the N≡N bond, whereas end-on adsorption favors localized metal-N2 interactions and shifts the potential-determining step to the initial N2 activation process. Furthermore, volcano-type relationships between the limiting potential and both the ICOHP-derived N2-DAC interaction strength and charge transfer to adsorbed N2 establish a quantitative structure-activity framework linking electronic structure with catalytic performance. Six Mo-TM@GDY (TM = Cr, Fe, Y, Hf, Ta, and Re) catalysts exhibit promising NRR activity, selectivity, and stability, with Mo-Cr@GDY delivering the highest activity at a limiting potential of -0.34 V. This work establishes a structure-activity framework linking electronic structure, N2 adsorption geometry, and catalytic performance, providing design principles for high-performance NRR electrocatalysts.
{"title":"Electronic Structure Engineering of Dual-Atom Catalysts Regulates N2 Adsorption Geometry for Enhanced Nitrogen Reduction","authors":"Mingyang Ren,Bingling He,Song Ye,Mengyin Liu,Shasha Li,Yongchun Li,Mengli Zhao,Peng Lv,Huan Li,Zhansheng Lu","doi":"10.1039/d6cp03490j","DOIUrl":"https://doi.org/10.1039/d6cp03490j","url":null,"abstract":"Understanding how electronic structure regulates N2 adsorption geometry is crucial for establishing structure-activity relationships in the nitrogen reduction reaction (NRR), yet the intrinsic relationship between electronic structure modulation and adsorption geometry remains poorly understood. Herein, density functional theory calculations are employed to investigate NRR on graphdiyne-supported Mo-TM dual-atom catalysts (Mo-TM@GDY, TM = 3d, 4d, and 5d transition metals). We demonstrate that the electronic structure of the secondary metal center drives a continuous transition of N2 adsorption geometry from side-on to end-on configurations across the Mo-TM@GDY series, accompanied by charge transfer to adsorbed N2 ranging from 0.19 to 0.97 e. This adsorption geometry transition governs N2 activation and reaction energetics, leading to distinct NRR pathways in which side-on adsorption promotes synergistic dual-metal activation of the N≡N bond, whereas end-on adsorption favors localized metal-N2 interactions and shifts the potential-determining step to the initial N2 activation process. Furthermore, volcano-type relationships between the limiting potential and both the ICOHP-derived N2-DAC interaction strength and charge transfer to adsorbed N2 establish a quantitative structure-activity framework linking electronic structure with catalytic performance. Six Mo-TM@GDY (TM = Cr, Fe, Y, Hf, Ta, and Re) catalysts exhibit promising NRR activity, selectivity, and stability, with Mo-Cr@GDY delivering the highest activity at a limiting potential of -0.34 V. This work establishes a structure-activity framework linking electronic structure, N2 adsorption geometry, and catalytic performance, providing design principles for high-performance NRR electrocatalysts.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"4 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The main focus of this work is to clarify how protein macromolecules become solvated in monohydric alcohols with low water content. Alcohols with varying hydrophobicity (1-propanol, ethanol, and methanol) were used as model organic liquids. Two independent experimental techniques (isothermal immersion calorimetry and water/alcohol adsorption) were employed to provide complementary thermodynamic functions of the preferential solvation of hen egg-white lysozyme in alcohols with low and high water contents at 298.15 K. The advantage of this approach is that the enthalpies and Gibbs energies of water and alcohols can be simultaneously studied during the deep dehydration of lysozyme. Three distinct composition regimes are operative in water–alcohol mixtures. Protein stabilization, as a result of the preferential hydration of lysozyme, was observed in the water-rich region, which was driven by a positive change in entropy, with the residual enzyme activity values close to 100%. Alcohol-induced inactivation of lysozyme was detected in the middle region, with the residual catalytic activity close to zero. In the water-poor region, the bulky ethanol and 1-propanol molecules, unlike methanol, were preferentially excluded from the protein surface. In the water-rich region, protein stabilization was driven by an exothermic (favorable) enthalpy change. The pairwise (adsorbate–adsorbate) interaction coefficients demonstrated that alcohols with longer alkyl chains stabilize water–water association at low water contents to a larger extent than methanol with a shorter alkyl chain. The results obtained may be highly relevant for elucidating the distinct roles of water bound to the amphiphilic surfaces of biomacromolecules.
{"title":"Lysozyme solvation in monohydric alcohols with low water content: a calorimetric and preferential solvation study","authors":"Vladimir A. Sirotkin","doi":"10.1039/d6cp01776b","DOIUrl":"https://doi.org/10.1039/d6cp01776b","url":null,"abstract":"The main focus of this work is to clarify how protein macromolecules become solvated in monohydric alcohols with low water content. Alcohols with varying hydrophobicity (1-propanol, ethanol, and methanol) were used as model organic liquids. Two independent experimental techniques (isothermal immersion calorimetry and water/alcohol adsorption) were employed to provide complementary thermodynamic functions of the preferential solvation of hen egg-white lysozyme in alcohols with low and high water contents at 298.15 K. The advantage of this approach is that the enthalpies and Gibbs energies of water and alcohols can be simultaneously studied during the deep dehydration of lysozyme. Three distinct composition regimes are operative in water–alcohol mixtures. Protein stabilization, as a result of the preferential hydration of lysozyme, was observed in the water-rich region, which was driven by a positive change in entropy, with the residual enzyme activity values close to 100%. Alcohol-induced inactivation of lysozyme was detected in the middle region, with the residual catalytic activity close to zero. In the water-poor region, the bulky ethanol and 1-propanol molecules, unlike methanol, were preferentially excluded from the protein surface. In the water-rich region, protein stabilization was driven by an exothermic (favorable) enthalpy change. The pairwise (adsorbate–adsorbate) interaction coefficients demonstrated that alcohols with longer alkyl chains stabilize water–water association at low water contents to a larger extent than methanol with a shorter alkyl chain. The results obtained may be highly relevant for elucidating the distinct roles of water bound to the amphiphilic surfaces of biomacromolecules.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"153 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225827","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The discovery of two-dimensional (2D) layered intrinsic magnets provides a new platform for designing high-efficiency nanoscale magnetic tunnel junctions (MTJs) based on 2D materials. In this work, based on Density Functional Theory associated with Non-Equilibrium Green's Function, we devised a novel 2D spin-filter (sf)-MTJ, namely the MoSe2/bilayer CrBr3/MoSe2 sf-MTJ using metallic MoSe2 as the electrode and bilayer CrBr3 semiconductor as the magnetic tunnel barrier. Compared with the commonly used 2D sf-MTJs based on few-layer CrI3, the proposed sf-MTJ features a simple structure, extremely thin thickness as well as good chemical stability. Spin transport calculations show that this newly-built sf-MTJ achieves almost perfect spin filtering efficiency (99.7 %) and enormous tunneling magnetoresistance ratio (TMR) up to 1.17 × 10^5 %. This excellent spin transport performance can be attributed to the strong spin-dependent transmission barrier effect in the sf-MTJ, which stems from the ferromagnetic half-metallicity of bilayer CrBr3 in parallel configuration induced by the substantial interfacial electron transfer between MoSe2 and CrBr3. In addition, it is found that when a small strain or bias voltage is applied, this new sf-MTJ maintains a favorable spin filtering effect (> 99 %) and a high TMR (~10^4 %). Our findings demonstrate that the MoSe2/bilayer CrBr3/MoSe2 sf-MTJ is a promising 2D spin-filter magnetic tunnel junction. This work also provides a new strategy for the design and fabrication of high-performance low-dimensional spintronic devices.
{"title":"Giant tunneling magnetoresistance in MoSe2/bilayer CrBr3/MoSe2 two-dimensional spin-filter magnetic tunnel junction","authors":"Jindi Feng,Zhihong Lu,Zhenhua Zhang,Rui Xiong","doi":"10.1039/d6cp03063g","DOIUrl":"https://doi.org/10.1039/d6cp03063g","url":null,"abstract":"The discovery of two-dimensional (2D) layered intrinsic magnets provides a new platform for designing high-efficiency nanoscale magnetic tunnel junctions (MTJs) based on 2D materials. In this work, based on Density Functional Theory associated with Non-Equilibrium Green's Function, we devised a novel 2D spin-filter (sf)-MTJ, namely the MoSe2/bilayer CrBr3/MoSe2 sf-MTJ using metallic MoSe2 as the electrode and bilayer CrBr3 semiconductor as the magnetic tunnel barrier. Compared with the commonly used 2D sf-MTJs based on few-layer CrI3, the proposed sf-MTJ features a simple structure, extremely thin thickness as well as good chemical stability. Spin transport calculations show that this newly-built sf-MTJ achieves almost perfect spin filtering efficiency (99.7 %) and enormous tunneling magnetoresistance ratio (TMR) up to 1.17 × 10^5 %. This excellent spin transport performance can be attributed to the strong spin-dependent transmission barrier effect in the sf-MTJ, which stems from the ferromagnetic half-metallicity of bilayer CrBr3 in parallel configuration induced by the substantial interfacial electron transfer between MoSe2 and CrBr3. In addition, it is found that when a small strain or bias voltage is applied, this new sf-MTJ maintains a favorable spin filtering effect (> 99 %) and a high TMR (~10^4 %). Our findings demonstrate that the MoSe2/bilayer CrBr3/MoSe2 sf-MTJ is a promising 2D spin-filter magnetic tunnel junction. This work also provides a new strategy for the design and fabrication of high-performance low-dimensional spintronic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"33 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225895","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We employ molecular dynamics simulations to investigate the capillary motion of liquid droplets within a nanopore featuring topographical and chemical heterogeneity along its longitudinal axis. The pore is divided into a structurally smooth region and a physically rough region composed of rectangular pillars with localized chemical variations at the pillar peaks. To modulate the wetting behavior, we introduce two-site dimeric solutes characterized by a solvent-like site and a tunable solid-like adsorption site. This architecture ensures that solutes selectively populate the solid-liquid interface, allowing us to tune the solid-liquid interfacial free energy while leaving the liquid-vapor interfacial free energy unchanged. Our results indicate that directional capillary motion can be triggered and even reversed between the smooth and rough regions through two distinct mechanisms: concentration-driven motion, where altering the bulk concentration of a single solute type shifts the droplet's thermodynamic propensity, and solute-type-driven motion, where modifying the chemical affinity of the solute at a constant concentration initiates translation. We also observed that unconfined rough surfaces allow higher solute concentrations to form a monolayer crust that physically bridges the gaps between adjacent pillars, maintaining a Cassie-Baxter-like wetting state even at low macroscopic contact angles. Conversely, nanopore confinement increases the accessible solid-liquid area, diluting solute coverage and allowing liquid to permeate the cavities. This transitions the system into a Wenzel-like state, pinning the three phase contact line and introducing kinetic barriers. Despite these barriers, these specialized neutral solutes act as passive agents for controlling complex nanoscale fluid transport.
{"title":"Concentration Driven Capillary Motion of Liquid Droplets Inside Chemically and Topographically Heterogeneous Nanopores","authors":"Prasad Baddi,Kaustubh Rane","doi":"10.1039/d6cp02234k","DOIUrl":"https://doi.org/10.1039/d6cp02234k","url":null,"abstract":"We employ molecular dynamics simulations to investigate the capillary motion of liquid droplets within a nanopore featuring topographical and chemical heterogeneity along its longitudinal axis. The pore is divided into a structurally smooth region and a physically rough region composed of rectangular pillars with localized chemical variations at the pillar peaks. To modulate the wetting behavior, we introduce two-site dimeric solutes characterized by a solvent-like site and a tunable solid-like adsorption site. This architecture ensures that solutes selectively populate the solid-liquid interface, allowing us to tune the solid-liquid interfacial free energy while leaving the liquid-vapor interfacial free energy unchanged. Our results indicate that directional capillary motion can be triggered and even reversed between the smooth and rough regions through two distinct mechanisms: concentration-driven motion, where altering the bulk concentration of a single solute type shifts the droplet's thermodynamic propensity, and solute-type-driven motion, where modifying the chemical affinity of the solute at a constant concentration initiates translation. We also observed that unconfined rough surfaces allow higher solute concentrations to form a monolayer crust that physically bridges the gaps between adjacent pillars, maintaining a Cassie-Baxter-like wetting state even at low macroscopic contact angles. Conversely, nanopore confinement increases the accessible solid-liquid area, diluting solute coverage and allowing liquid to permeate the cavities. This transitions the system into a Wenzel-like state, pinning the three phase contact line and introducing kinetic barriers. Despite these barriers, these specialized neutral solutes act as passive agents for controlling complex nanoscale fluid transport.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"15 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nonadiabatic dynamics of Na3 are strongly influenced by an E′ Jahn-Teller conical intersection seam at D3h geometries. Here, we construct a D3h symmetry-adapted two-state quasi-diabatic Hamiltonian for Na3 from ab initio adiabatic energies alone. Fundamental invariants and symmetry-covariant basis functions impose permutation symmetry and the symmetry-required conical intersection structure, while three scalar fundamental invariant neural-network functions describe the coordinate dependence of the Hamiltonian elements. The resulting quasi-diabatic matrix elements are smooth, and diagonalization reproduces the ab initio ground-and excited-state energies with rootmean-square errors of 4.6 × 10-5 and 1.5 × 10-4 eV, respectively. The fitted quasidiabatic potential energy matrix is applied to Na + Na2(v = 0, j = 0) quantum scattering. Comparison with adiabatic calculations shows that the geometric phase (GP) substantially modifies the resonance structure, while the remaining differences suggest a role for excited-state participation in the reaction dynamics. This work provides an energy-only route to quasi-diabatic Hamiltonians that incorporate molecular symmetry for nonadiabatic dynamics in metal trimers.
{"title":"Energy-Only Construction of a Symmetry-Adapted Quasi-Diabatic Hamiltonian for the Two Lowest States of Na","authors":"Baihui Feng,Yuegu Fang,Jiayu Huang","doi":"10.1039/d6cp02697d","DOIUrl":"https://doi.org/10.1039/d6cp02697d","url":null,"abstract":"Nonadiabatic dynamics of Na3 are strongly influenced by an E′ Jahn-Teller conical intersection seam at D3h geometries. Here, we construct a D3h symmetry-adapted two-state quasi-diabatic Hamiltonian for Na3 from ab initio adiabatic energies alone. Fundamental invariants and symmetry-covariant basis functions impose permutation symmetry and the symmetry-required conical intersection structure, while three scalar fundamental invariant neural-network functions describe the coordinate dependence of the Hamiltonian elements. The resulting quasi-diabatic matrix elements are smooth, and diagonalization reproduces the ab initio ground-and excited-state energies with rootmean-square errors of 4.6 × 10-5 and 1.5 × 10-4 eV, respectively. The fitted quasidiabatic potential energy matrix is applied to Na + Na2(v = 0, j = 0) quantum scattering. Comparison with adiabatic calculations shows that the geometric phase (GP) substantially modifies the resonance structure, while the remaining differences suggest a role for excited-state participation in the reaction dynamics. This work provides an energy-only route to quasi-diabatic Hamiltonians that incorporate molecular symmetry for nonadiabatic dynamics in metal trimers.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"3 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rongjian Sa,Liangchun Wu,Linfeng Hu,Xintian Chen,Helong Wu,Weiguo Li,Zuju Ma,Yuan Hu
Electrocatalytic nitrogen reduction (NRR) offers a sustainable route for ammonia synthesis at room temperature, but is limited by sluggish N2 activation and the competing hydrogen evolution reaction (HER). We systematically evaluated 18 FeM@g-C6N6 diatomic catalysts using density functional theory (DFT) calculations.Through stepwise screening based on stability, N2 adsorption strength, HER suppression, and first-step hydrogenation free-energy changes, 12 promising candidates were identified. Among them, Fe-EB exhibited the best performance via a distal pathway, with a limiting potential of -0.44 V, followed by Tc-ES (-0.45 V) and Ta-SD (-0.46 V). Electronic structure analysis indicates that N2 activation stems from electron donation to the π* orbital and orbital hybridization between N p orbitals and the metal d orbitals. Descriptor analysis further reveals that the degree of N2 activation can be rationalized by the metal d-band center, which correlates linearly with the N≡N ICOHP (R 2 = 0.93), and by the charge donated to N2, which scales with the N≡N bond elongation (R 2 = 0.92). Adjacent * OH co-adsorption, used to approximate a hydroxylated local adsorbate environment, influences the reaction pathways and activity of the catalyst but does not alter its fundamental activation mechanism. This study provides useful mechanistic insights and descriptors for the rational design of g-C₆N₆-based diatomic NRR catalysts.
{"title":"Computational Screening of FeM@g-C 6 N 6 Diatomic Catalysts for Selective Electrocatalytic Nitrogen Reduction","authors":"Rongjian Sa,Liangchun Wu,Linfeng Hu,Xintian Chen,Helong Wu,Weiguo Li,Zuju Ma,Yuan Hu","doi":"10.1039/d6cp02439d","DOIUrl":"https://doi.org/10.1039/d6cp02439d","url":null,"abstract":"Electrocatalytic nitrogen reduction (NRR) offers a sustainable route for ammonia synthesis at room temperature, but is limited by sluggish N2 activation and the competing hydrogen evolution reaction (HER). We systematically evaluated 18 FeM@g-C6N6 diatomic catalysts using density functional theory (DFT) calculations.Through stepwise screening based on stability, N2 adsorption strength, HER suppression, and first-step hydrogenation free-energy changes, 12 promising candidates were identified. Among them, Fe-EB exhibited the best performance via a distal pathway, with a limiting potential of -0.44 V, followed by Tc-ES (-0.45 V) and Ta-SD (-0.46 V). Electronic structure analysis indicates that N2 activation stems from electron donation to the π* orbital and orbital hybridization between N p orbitals and the metal d orbitals. Descriptor analysis further reveals that the degree of N2 activation can be rationalized by the metal d-band center, which correlates linearly with the N≡N ICOHP (R 2 = 0.93), and by the charge donated to N2, which scales with the N≡N bond elongation (R 2 = 0.92). Adjacent * OH co-adsorption, used to approximate a hydroxylated local adsorbate environment, influences the reaction pathways and activity of the catalyst but does not alter its fundamental activation mechanism. This study provides useful mechanistic insights and descriptors for the rational design of g-C₆N₆-based diatomic NRR catalysts.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225821","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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