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}
Thermoelectric power is an efficient and flexible technology for improving energy efficiency, but widespread applications require cost-effective and sustainable materials with a high figure of merit zT. Alloying is a common strategy for optimising zT, but predicting and understanding its impact on the material properties is made challenging by the structural disorder. In this work, we develop a practical and rigorous approach to predicting the zT of alloys by combining first-principles electrical-transport and lattice thermal-conductivity calculations, with approximate models for the electron and phonon scattering, and apply it to study the Sn(S0.2Se0.8) alloy. We compare predictions obtained by averaging over the full set of unique configurations in a 32-atom supercell with those obtained from special quasi-random structure (SQS) structures with supercell sizes of up to 256 atoms. We find that a 128-atom SQS model provides good computational efficiency while avoiding supercell size artifacts, and yields realistic predictions of the physical properties at the extrinsic carrier concentrations ("doping levels") that optimise the zT. The calculations indicate that Sn(S0.2Se0.8) shows comparable performance to the SnSe endpoint but with a modest enhancement to the zT due to a reduction in the lattice thermal conductivity, which has a particularly significant impact on the low-temperature performance.
{"title":"First-principles prediction of the thermoelectric properties of Sn(S0.2Se0.8) alloys","authors":"Min Zhang,Joseph Flitcroft,Jonathan Skelton","doi":"10.1039/d6cp02931k","DOIUrl":"https://doi.org/10.1039/d6cp02931k","url":null,"abstract":"Thermoelectric power is an efficient and flexible technology for improving energy efficiency, but widespread applications require cost-effective and sustainable materials with a high figure of merit zT. Alloying is a common strategy for optimising zT, but predicting and understanding its impact on the material properties is made challenging by the structural disorder. In this work, we develop a practical and rigorous approach to predicting the zT of alloys by combining first-principles electrical-transport and lattice thermal-conductivity calculations, with approximate models for the electron and phonon scattering, and apply it to study the Sn(S0.2Se0.8) alloy. We compare predictions obtained by averaging over the full set of unique configurations in a 32-atom supercell with those obtained from special quasi-random structure (SQS) structures with supercell sizes of up to 256 atoms. We find that a 128-atom SQS model provides good computational efficiency while avoiding supercell size artifacts, and yields realistic predictions of the physical properties at the extrinsic carrier concentrations (\"doping levels\") that optimise the zT. The calculations indicate that Sn(S0.2Se0.8) shows comparable performance to the SnSe endpoint but with a modest enhancement to the zT due to a reduction in the lattice thermal conductivity, which has a particularly significant impact on the low-temperature performance.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"13 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218284","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 two-dimensional polymeric material graphitic carbon nitride (gCN) has remarkable stability with application in photothermal therapy and drug delivery. When nanomaterials encounter proteins, they can lead to protein adsorption on their surfaces or the development of a protein corona. Such interaction could either influence or impair the biological roles of proteins. In this study, the time-dependent interaction between graphitic carbon nitride sheet-like nanorods (gCN NRs) and human serum albumin (HSA) was investigated to elucidate the molecular mechanism of protein adsorption and corona evolution. Steady-state and time-resolved fluorescence spectroscopy, circular dichroism spectroscopy, isothermal titration calorimetry and differential scanning calorimetry were employed to characterize the binding process, conformational changes, and thermodynamic aspects of the interaction. The results reveal that HSA initially binds to the surface of gCN nanorods (NRs) through weak interactions with minimal conformational changes.However, the adsorbed protein continues to undergo structural rearrangements over time, leading to significant alterations in its secondary and tertiary structure. Furthermore, the drug loading and delivery of gCN NR was studied with the hydrophobic drug quercetin which altered the surface properties of the nanorods and resulted in enhanced interaction with HSA. These findings provide mechanistic insight into the adsorption behaviour, conformational evolution, and protein corona formation of HSA on gCN NRs.
{"title":"Protein Adsorption and Drug Delivery Potential of Graphitic Carbon Nitride Nanorods: Physicochemical Insights with Human Serum Albumin and Quercetin","authors":"Catherine Pasangha,Nand Kishore","doi":"10.1039/d6cp02919a","DOIUrl":"https://doi.org/10.1039/d6cp02919a","url":null,"abstract":"The two-dimensional polymeric material graphitic carbon nitride (gCN) has remarkable stability with application in photothermal therapy and drug delivery. When nanomaterials encounter proteins, they can lead to protein adsorption on their surfaces or the development of a protein corona. Such interaction could either influence or impair the biological roles of proteins. In this study, the time-dependent interaction between graphitic carbon nitride sheet-like nanorods (gCN NRs) and human serum albumin (HSA) was investigated to elucidate the molecular mechanism of protein adsorption and corona evolution. Steady-state and time-resolved fluorescence spectroscopy, circular dichroism spectroscopy, isothermal titration calorimetry and differential scanning calorimetry were employed to characterize the binding process, conformational changes, and thermodynamic aspects of the interaction. The results reveal that HSA initially binds to the surface of gCN nanorods (NRs) through weak interactions with minimal conformational changes.However, the adsorbed protein continues to undergo structural rearrangements over time, leading to significant alterations in its secondary and tertiary structure. Furthermore, the drug loading and delivery of gCN NR was studied with the hydrophobic drug quercetin which altered the surface properties of the nanorods and resulted in enhanced interaction with HSA. These findings provide mechanistic insight into the adsorption behaviour, conformational evolution, and protein corona formation of HSA on gCN NRs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"79 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218289","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}
Olga Selyutina,Nikolay Polyakov,Alexander S Molokoedov,Maria V Sidorova,Dmitry Avdeev
The stereoselectivity of chiral drug interactions with enzymatic active sites and cellular receptors is a subject of significant scientific interest. This interest is driven, firstly, by the pronounced differences in the therapeutic activity of drug enantiomers and, secondly, by the emerging role of amino acid chiral inversion in peptides associated with pathologies such as Alzheimer's, Parkinson's, and type II diabetes. To probe the fundamental steps of such biomolecular interactions, electron transfer (ET) serves as a well-defined elementary chemical process. Prior investigations of photoinduced ET in chiral donor-acceptor dyads, incorporating (S)-ketoprofen and (L/D)-tryptophan, have revealed stereoselective and spin-selective phenomena. Extending this work, the present study examines the interaction of (S)-ketoprofen with the L- and D-enantiomers of tryptophan within the tetrapeptide Tryptophan-Leucine-Proline-Phenylalanine (WLPF), in homogeneous non-aqueous solutions. Utilizing NMR spectroscopy, chemically induced dynamic nuclear polarization (CIDNP) to detect transient paramagnetic intermediates, and molecular modeling, we have demonstrated that (S)-ketoprofen exhibits stereoselective interaction with the peptide epimers. Furthermore, it was shown that the D-epimer of the peptide has a greater tendency to aggregation than the L-epimer. The stereoselective light-induced formation of the ketoprofen ketyl radicals provides a plausible mechanistic basis for ketoprofen's phototoxic side effects.
{"title":"Stereoselectivity of photoinduced interaction of nonsteroidal anti-inflammatory drug S-ketoprofen with (L/D)-Trp-Leu-Pro-Phe peptide in solution studied by NMR, CIDNP and molecular dynamics simulation","authors":"Olga Selyutina,Nikolay Polyakov,Alexander S Molokoedov,Maria V Sidorova,Dmitry Avdeev","doi":"10.1039/d6cp02914k","DOIUrl":"https://doi.org/10.1039/d6cp02914k","url":null,"abstract":"The stereoselectivity of chiral drug interactions with enzymatic active sites and cellular receptors is a subject of significant scientific interest. This interest is driven, firstly, by the pronounced differences in the therapeutic activity of drug enantiomers and, secondly, by the emerging role of amino acid chiral inversion in peptides associated with pathologies such as Alzheimer's, Parkinson's, and type II diabetes. To probe the fundamental steps of such biomolecular interactions, electron transfer (ET) serves as a well-defined elementary chemical process. Prior investigations of photoinduced ET in chiral donor-acceptor dyads, incorporating (S)-ketoprofen and (L/D)-tryptophan, have revealed stereoselective and spin-selective phenomena. Extending this work, the present study examines the interaction of (S)-ketoprofen with the L- and D-enantiomers of tryptophan within the tetrapeptide Tryptophan-Leucine-Proline-Phenylalanine (WLPF), in homogeneous non-aqueous solutions. Utilizing NMR spectroscopy, chemically induced dynamic nuclear polarization (CIDNP) to detect transient paramagnetic intermediates, and molecular modeling, we have demonstrated that (S)-ketoprofen exhibits stereoselective interaction with the peptide epimers. Furthermore, it was shown that the D-epimer of the peptide has a greater tendency to aggregation than the L-epimer. The stereoselective light-induced formation of the ketoprofen ketyl radicals provides a plausible mechanistic basis for ketoprofen's phototoxic side effects.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"311 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218281","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}
Tomonori Izu,Kien Xuan Vo,Keisuke Hirata,Masaaki Fujii,Shun-ichi Ishiuchi,Anne Zehnacker
The Copper(II)-Proline-L-Tyrosine and Copper(II)-Proline-D-Tyrosine complex ions, denoted as LL and LD, play an important role in chiral ligand-exchange chromatography (CLEC). These singly charged complexes, containing one neutral and one anionic amino acid ligand, have been isolated in a cryogenic ion trap and characterised by laser spectroscopy in the 3 µm and fingerprint regions. The two diastereomers can be clearly differentiated by their vibrational spectra. Two different isomers for LL and three for LD are deduced from IR-IR hole burning spectra. Quantum chemical calculations show that LL and LD both exist in two square planar structures involving deprotonation of Tyr for one of them or Pro for the other. Although similar in nature, the corresponding LL and LD structures differ by the relative position of the Tyr aromatic ring and the Pro ring, which are on the same side of the N/O…Cu…N/O plane for LL and on opposite sides for LD. They also differ by the puckering state, endo or exo, of the proline ring. In addition, the LD complex stands out by the presence of a kinetically trapped structure that contains Pro in its zwitterion form, with a very characteristic spectroscopic signature. This finding confirms the role of zwitterionic structures in the chemistry of copper clusters of amino acids.
铜(II)-脯氨酸- l -酪氨酸和铜(II)-脯氨酸- d-酪氨酸络合离子分别记为LL和LD，在手性配体交换色谱（CLEC）中起重要作用。这些单电荷的配合物，包含一个中性和一个阴离子氨基酸配体，在低温离子阱中被分离出来，并在3µm和指纹区用激光光谱进行了表征。这两种非对映体可以通过它们的振动谱清楚地加以区分。从IR-IR空穴燃烧光谱中推导出了LL的两种异构体和LD的三种异构体。量子化学计算表明，LL和LD都存在于两个方形平面结构中，其中一个是Tyr去质子化，另一个是Pro去质子化。虽然性质相似，但LL和LD结构的不同之处在于Tyr环和Pro环的相对位置，LL的Tyr环和Pro环在N/O…Cu…N/O平面的同一侧，LD的Pro环在N/O平面的相反一侧，它们的脯氨酸环的皱缩状态（内或外）也不同。此外，LD配合物的突出之处在于其含有双阴离子形式的Pro的动力学捕获结构，具有非常独特的光谱特征。这一发现证实了两性离子结构在氨基酸铜簇化学中的作用。
{"title":"Probing Chiral Chromatography Systems in Vacuo: Cryogenic Ion Trap Laser Spectroscopy of Diastereomeric Copper(II)-Proline-Tyrosine Complexes.","authors":"Tomonori Izu,Kien Xuan Vo,Keisuke Hirata,Masaaki Fujii,Shun-ichi Ishiuchi,Anne Zehnacker","doi":"10.1039/d6cp03233h","DOIUrl":"https://doi.org/10.1039/d6cp03233h","url":null,"abstract":"The Copper(II)-Proline-L-Tyrosine and Copper(II)-Proline-D-Tyrosine complex ions, denoted as LL and LD, play an important role in chiral ligand-exchange chromatography (CLEC). These singly charged complexes, containing one neutral and one anionic amino acid ligand, have been isolated in a cryogenic ion trap and characterised by laser spectroscopy in the 3 µm and fingerprint regions. The two diastereomers can be clearly differentiated by their vibrational spectra. Two different isomers for LL and three for LD are deduced from IR-IR hole burning spectra. Quantum chemical calculations show that LL and LD both exist in two square planar structures involving deprotonation of Tyr for one of them or Pro for the other. Although similar in nature, the corresponding LL and LD structures differ by the relative position of the Tyr aromatic ring and the Pro ring, which are on the same side of the N/O…Cu…N/O plane for LL and on opposite sides for LD. They also differ by the puckering state, endo or exo, of the proline ring. In addition, the LD complex stands out by the presence of a kinetically trapped structure that contains Pro in its zwitterion form, with a very characteristic spectroscopic signature. This finding confirms the role of zwitterionic structures in the chemistry of copper clusters of amino acids.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"58 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218282","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}
Anthracene-based compounds capable of photocycloaddition reaction have garnered extensive attention for the fabrication of light-responsive crystalline materials. Nevertheless, their solid-state photocycloaddition mechanism remains elusive. Herein, transient absorption spectroscopy combined with theoretical calculations was employed to elucidate the cycloaddition mechanism of monoclinic 9-anthracenecarboxylic acid (9AC) crystal, which possesses head-to-head cofacially stacked anthracene dimers. It is found that the photodimerization of 9AC proceeds via a stepwise mechanism in the triplet state. This is supported by the the first-observed rapid population and decay of excited state absorption signal from triplet state. During excited-state dynamical evolution, the locally excited S1 state first rapidly relaxes to a delocalized S1 state.Subsequently, an efficient intersystem crossing process occurs at the S1/T2 crossing point, followed by internal conversion to the T1 state. Next, the crossing of a transition state facilitates the first C-C bond formation and generates a diradical intermediate. Finally, the second C-C bond is formed through the transition of the diradical intermediate to the cycloaddition product via the T1/S0 crossing point. Notably, the final step is promoted by the intermolecular hydrogen bonds that constrain the rotational variations between two anthracene units. Besides, the transition state acts as a singlet-triplet crossing point and forms an unfavorable energy dissipation channel, accounting for the slow cycloaddition rate of 9AC. This finding provides an unambiguous insight into the solid-state [4+4] photocycloaddition mechanism, which is essential for the rational design and development of anthracene-based smart materials.
{"title":"Unveiling the excited-state cycloaddition mechanism of crystalline 9-anthracenecarboxylic acid via transient absorption spectroscopy and theoretical calculations","authors":"Ming Zhu,Yan-Xiang Chen,Yi-Lan Fan,Zi-Chen Liao,Shaofei Ni,Wenbin Chen,Li Dang,Ming-De Li,Shun-Li Chen,Xin-Da Huang","doi":"10.1039/d6cp03469a","DOIUrl":"https://doi.org/10.1039/d6cp03469a","url":null,"abstract":"Anthracene-based compounds capable of photocycloaddition reaction have garnered extensive attention for the fabrication of light-responsive crystalline materials. Nevertheless, their solid-state photocycloaddition mechanism remains elusive. Herein, transient absorption spectroscopy combined with theoretical calculations was employed to elucidate the cycloaddition mechanism of monoclinic 9-anthracenecarboxylic acid (9AC) crystal, which possesses head-to-head cofacially stacked anthracene dimers. It is found that the photodimerization of 9AC proceeds via a stepwise mechanism in the triplet state. This is supported by the the first-observed rapid population and decay of excited state absorption signal from triplet state. During excited-state dynamical evolution, the locally excited S1 state first rapidly relaxes to a delocalized S1 state.Subsequently, an efficient intersystem crossing process occurs at the S1/T2 crossing point, followed by internal conversion to the T1 state. Next, the crossing of a transition state facilitates the first C-C bond formation and generates a diradical intermediate. Finally, the second C-C bond is formed through the transition of the diradical intermediate to the cycloaddition product via the T1/S0 crossing point. Notably, the final step is promoted by the intermolecular hydrogen bonds that constrain the rotational variations between two anthracene units. Besides, the transition state acts as a singlet-triplet crossing point and forms an unfavorable energy dissipation channel, accounting for the slow cycloaddition rate of 9AC. This finding provides an unambiguous insight into the solid-state [4+4] photocycloaddition mechanism, which is essential for the rational design and development of anthracene-based smart materials.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"83 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218279","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}
Janus transition-metal dihalide monolayers represent an emerging class of twodimensional semiconductors with intrinsic out-of-plane asymmetry, yet their systematic compositional exploration remains limited. We report a comprehensive first-principles study of Janus BrClM (M = Ti, Zr, Hf) monolayers combining density functional theory, hybrid-functional Heyd-Scuseria-Ernzerhof (HSE06) calculations with spin-orbit coupling (SOC), and many-body GW approximation with the Bethe-Salpeter equation (G₀W₀-BSE) optical spectroscopy. All three monolayers are dynamically and mechanically stable semiconductors with band gaps tunable from 1.22 eV (near-direct, BrClTi) to 1.52 eV (indirect, BrClHf) via Group IV-B metal substitution. Asymmetric Br/Cl termination drives unequal charge redistribution, generating intrinsic dipoles, pronounced surface-dependent work functions, and vacuum-aligned band edges that differ on the Br-and Cl-terminated sides; SOC electrostatic validation confirms the robustness of this interfacial asymmetry. Many-body optical analysis reveals strong absorption (~10⁵ cm⁻¹) spanning infrared-visible to visible-ultraviolet regimes, alongside exciton binding energies of ~0.58 eV (BrClTi) ~0.64 eV (BrClZr) and ~ 0.26 eV (BrClHf) that signify strongly bound two-dimensional excitons. A higher-order equivariant message-passing neural network (MACE) based machine-learned interatomic potential provides restricteddomain finite-temperature and phonon-displacement support. These findings establish Janus BrClM monolayers as composition-tunable platforms for ultrathin optoelectronic and excitonic devices.
双面过渡金属二卤化物单层代表了一类新兴的二维半导体，具有固有的面外不对称性，但其系统的成分探索仍然有限。本文报道了结合密度泛函理论、混合泛函Heyd-Scuseria-Ernzerhof （HSE06）计算和Bethe-Salpeter方程（G 0 W 0 -BSE）光谱学的多体GW近似，对Janus BrClM （M = Ti, Zr, Hf）单层进行了全面的第一性原理研究。这三种单层膜都是动态和机械稳定的半导体，其带隙可通过IV-B族金属取代从1.22 eV（近直接BrClTi）到1.52 eV（间接BrClHf）调节。不对称的Br/Cl终止驱动不均匀的电荷再分配，产生本征偶极子，明显的表面依赖功函数，以及Br端和Cl端不同的真空对准带边；SOC静电验证证实了这种界面不对称性的稳健性。多体光学分析显示，强吸收（~10 5 cm⁻¹）跨越红外-可见光到可见-紫外波段，激子结合能为~0.58 eV (BrClTi) ~0.64 eV （BrClZr）和~ 0.26 eV (BrClHf)，表明二维激子的结合能很强。基于机器学习的高阶等变消息传递神经网络（MACE）提供了限制域有限温度和声子位移支持。这些发现确立了Janus BrClM单层作为超薄光电和激子器件的成分可调平台。
{"title":"Janus BrClM (M = Ti, Zr, Hf) Monolayers: First-Principles Insights and a Restricted-Domain Machine-Learned Potential Analysis of Band Gaps, Surface Dipoles, and Optical Response Across the Group IV–B Series","authors":"Babar Ali,Ahsan Javed,Muhammad Ali,Zijing Lin","doi":"10.1039/d6cp03121h","DOIUrl":"https://doi.org/10.1039/d6cp03121h","url":null,"abstract":"Janus transition-metal dihalide monolayers represent an emerging class of twodimensional semiconductors with intrinsic out-of-plane asymmetry, yet their systematic compositional exploration remains limited. We report a comprehensive first-principles study of Janus BrClM (M = Ti, Zr, Hf) monolayers combining density functional theory, hybrid-functional Heyd-Scuseria-Ernzerhof (HSE06) calculations with spin-orbit coupling (SOC), and many-body GW approximation with the Bethe-Salpeter equation (G₀W₀-BSE) optical spectroscopy. All three monolayers are dynamically and mechanically stable semiconductors with band gaps tunable from 1.22 eV (near-direct, BrClTi) to 1.52 eV (indirect, BrClHf) via Group IV-B metal substitution. Asymmetric Br/Cl termination drives unequal charge redistribution, generating intrinsic dipoles, pronounced surface-dependent work functions, and vacuum-aligned band edges that differ on the Br-and Cl-terminated sides; SOC electrostatic validation confirms the robustness of this interfacial asymmetry. Many-body optical analysis reveals strong absorption (~10⁵ cm⁻¹) spanning infrared-visible to visible-ultraviolet regimes, alongside exciton binding energies of ~0.58 eV (BrClTi) ~0.64 eV (BrClZr) and ~ 0.26 eV (BrClHf) that signify strongly bound two-dimensional excitons. A higher-order equivariant message-passing neural network (MACE) based machine-learned interatomic potential provides restricteddomain finite-temperature and phonon-displacement support. These findings establish Janus BrClM monolayers as composition-tunable platforms for ultrathin optoelectronic and excitonic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"42 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218283","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}
In botany, phyllotactic structures are typically regular, spiraled arrangements of leaves, flowers, or other plant organs that grow around a stem. Phyllotactic-like patterns can also be obtained when a reactant of a precipitation reaction is radially injected at a given flow rate in a confined geometry containing the other reactant. Here, we analyze the properties of such spiraled precipitation patterns produced experimentally in the wake of a radially moving reaction front. Specifically, we inject an aqueous solution of sodium carbonate into a solution of barium chloride, or vice versa, and analyze the symmetries of the barium carbonate precipitation patterns. We find that, in a given zone of the parameter space, phyllotactic structures are reproducibly observed. The number of parastichies constructing the symmetry of the pattern varies with injection flow rate, concentrations of the reactant solutions, and buoyancy.
{"title":"Experimental phyllotactic patterns in the wake of radially moving chemical precipitation fronts","authors":"G. Schuszter,M. Olasz,F. Brau,A. De Wit","doi":"10.1039/d6cp02952c","DOIUrl":"https://doi.org/10.1039/d6cp02952c","url":null,"abstract":"In botany, phyllotactic structures are typically regular, spiraled arrangements of leaves, flowers, or other plant organs that grow around a stem. Phyllotactic-like patterns can also be obtained when a reactant of a precipitation reaction is radially injected at a given flow rate in a confined geometry containing the other reactant. Here, we analyze the properties of such spiraled precipitation patterns produced experimentally in the wake of a radially moving reaction front. Specifically, we inject an aqueous solution of sodium carbonate into a solution of barium chloride, or vice versa, and analyze the symmetries of the barium carbonate precipitation patterns. We find that, in a given zone of the parameter space, phyllotactic structures are reproducibly observed. The number of parastichies constructing the symmetry of the pattern varies with injection flow rate, concentrations of the reactant solutions, and buoyancy.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"88 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218288","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}
As the solid metal with the lowest atomic number, lithium is a typical material for investigating electronic stopping power. We investigate the electronic stopping power of lithium nanosheets for protons using real-time time-dependent density functional theory combined with Ehrenfest molecular dynamics simulations. To elucidate the role of core electrons in the energy dissipation process, we systematically compare two pseudopotential models for Li: one including only valence electrons (Li[2s1 ]) and another including core electrons (Li[1s2 2s1 ]), for both channeling and off-channeling trajectories. The results indicate that in the low-velocity regime (v ≤ 0.2 a.u.), the energy transferred by the proton is insufficient to excite the 1s core electrons; the S e is entirely dominated by valence electrons, and is insensitive to the incident trajectory. When the velocity exceeds the threshold, the contribution of core electrons gradually emerges: in the intermediate velocity regime, dynamic polarization of the electron cloud serves as the main channel to indirectly boost valence-electron excitation; at high velocity (v = 1.0 a.u.), direct ionization of 1s electrons occurs, serving as a dominant energy dissipation channel. In addition, chemical-bond formation and charge capture serve as supplementary dissipation mechanisms, with the electron-capture effect being most pronounced at a proton velocity of 0.6 a.u. This study elucidates the contribution of core electrons to the Se in lithium and provides a theoretical basis for assessing irradiation damage in lithium materials used in fusion devices.
{"title":"Effects of core electrons on electronic stopping power in proton-irradiated lithium nanosheets","authors":"Su-Na Pang,Ya-Ting Sun,Feng Wang","doi":"10.1039/d6cp02834a","DOIUrl":"https://doi.org/10.1039/d6cp02834a","url":null,"abstract":"As the solid metal with the lowest atomic number, lithium is a typical material for investigating electronic stopping power. We investigate the electronic stopping power of lithium nanosheets for protons using real-time time-dependent density functional theory combined with Ehrenfest molecular dynamics simulations. To elucidate the role of core electrons in the energy dissipation process, we systematically compare two pseudopotential models for Li: one including only valence electrons (Li[2s1 ]) and another including core electrons (Li[1s2 2s1 ]), for both channeling and off-channeling trajectories. The results indicate that in the low-velocity regime (v ≤ 0.2 a.u.), the energy transferred by the proton is insufficient to excite the 1s core electrons; the S e is entirely dominated by valence electrons, and is insensitive to the incident trajectory. When the velocity exceeds the threshold, the contribution of core electrons gradually emerges: in the intermediate velocity regime, dynamic polarization of the electron cloud serves as the main channel to indirectly boost valence-electron excitation; at high velocity (v = 1.0 a.u.), direct ionization of 1s electrons occurs, serving as a dominant energy dissipation channel. In addition, chemical-bond formation and charge capture serve as supplementary dissipation mechanisms, with the electron-capture effect being most pronounced at a proton velocity of 0.6 a.u. This study elucidates the contribution of core electrons to the Se in lithium and provides a theoretical basis for assessing irradiation damage in lithium materials used in fusion devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"163 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218277","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}
Chao Yu,Cheng Tang,Man Yin,Song Qin,Ling He,Guo-Hong Tao
The ionic polyimine network (IPIN) derived from choline lysinate ionic liquid possesses multiple iodine adsorption sites, including ionic groups, Schiff base structures, and imine groups. Through the polarization effect and charge redistribution induced by the electric field, IPIN exhibits a high retention rate more than 99% for flowing iodine gas.
{"title":"Enhanced iodine capture performance by ionic polyimine network materials in electric field †","authors":"Chao Yu,Cheng Tang,Man Yin,Song Qin,Ling He,Guo-Hong Tao","doi":"10.1039/d6cp02945k","DOIUrl":"https://doi.org/10.1039/d6cp02945k","url":null,"abstract":"The ionic polyimine network (IPIN) derived from choline lysinate ionic liquid possesses multiple iodine adsorption sites, including ionic groups, Schiff base structures, and imine groups. Through the polarization effect and charge redistribution induced by the electric field, IPIN exhibits a high retention rate more than 99% for flowing iodine gas.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"64 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218285","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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