Physical Chemistry Chemical Physics最新文献_第3页

Computational Screening of FeM@g-C 6 N 6 Diatomic Catalysts for Selective Electrocatalytic Nitrogen Reduction FeM@g-C 6 n6双原子选择性电催化氮还原催化剂的计算筛选

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-10-20 DOI: 10.1039/d6cp02439d

Rongjian Sa,Liangchun Wu,Linfeng Hu,Xintian Chen,Helong Wu,Weiguo Li,Zuju Ma,Yuan Hu

{"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}

引用次数: 0

Differential effects of rattling-like behavior on the thermoelectric transport properties of KSnX (X = Bi, P) under the influence of lone-pair electrons 孤对电子影响下KSnX （X = Bi， P）的类摇铃行为对热电输运性质的差分效应

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-10-20 DOI: 10.1039/d6cp02491b

Ran Zhang,Yinchang Zhao,Junping Wang,Jun Ni,Zhenhong Dai

引用次数: 0

A non-resonant Kβ valence-to-core X-ray emission approach for fluorine and oxygen differentiation in Zr compounds. Zr化合物中氟和氧分化的非共振Kβ价核x射线发射方法。

IF 3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-10-20 DOI: 10.1039/d6cp01440b

Christian Heinekamp, C Tufan Cakir, Ana Guilherme Buzanich, Konstantin Klementiev, Michael Roemelt, Thomas Braun, Franziska Emmerling

{"title":"A non-resonant Kβ valence-to-core X-ray emission approach for fluorine and oxygen differentiation in Zr compounds.","authors":"Christian Heinekamp, C Tufan Cakir, Ana Guilherme Buzanich, Konstantin Klementiev, Michael Roemelt, Thomas Braun, Franziska Emmerling","doi":"10.1039/d6cp01440b","DOIUrl":"https://doi.org/10.1039/d6cp01440b","url":null,"abstract":"Valence-to-core (VtC) X-ray emission spectroscopy (XES) is a powerful probe for the local electronic structure in transition-metal materials, but its potential for 4d metals such as zirconium remains largely unexplored. Here, we demonstrate that non-resonant Zr Kβ VtC XES provides quantitative descriptors that are sensitive to ligand chemistry, by probing fluorine- and oxygen-based coordination environments in well-defined and catalytically relevant Zr compounds. High-resolution X-ray emission spectra containing Zr-Kβ2 and -Kβ4 are recorded for a series of reference systems (ZrO2, ZrF4, ZrF4·H2O, ZrCl4, Zr(acac)4, Zr metal) and for Zr fluoride materials, and are analysed using quantitative line-shape parameters. Projected densities of states (PDOS) obtained from FDMNES calculations reveal that fluorine coordination enhances the Kβ″ contribution and induces characteristic changes in Kβ2 intensity and asymmetry compared to oxygen and chlorine ligands. These ligand-specific spectral signatures enable a systematic discrimination between F- and O-containing coordination spheres, even when conventional X-ray absorption or diffraction techniques provide limited contrast. This combined experimental-computational framework demonstrates that Zr Kβ VtC XES can resolve subtle ligand-dependent coordination changes in Zr-based materials, offering a general route to identify active structures in C-F bond activation and oxygen-evolution catalysis.","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":"149222889","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}

引用次数: 0

MXene-functionalized SWCNT/polyurethane nanocomposite for flexible thermoelectric module 用于柔性热电模块的碳纳米管/聚氨酯纳米复合材料

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-10-20 DOI: 10.1039/d6cp02941h

Saurabh Kumar Jha,Priyam Srivastava,Beate Krause,Rani Rohini

{"title":"MXene-functionalized SWCNT/polyurethane nanocomposite for flexible thermoelectric module","authors":"Saurabh Kumar Jha,Priyam Srivastava,Beate Krause,Rani Rohini","doi":"10.1039/d6cp02941h","DOIUrl":"https://doi.org/10.1039/d6cp02941h","url":null,"abstract":"Single-walled carbon nanotubes (SWCNT) are efficient materials for thermoelectric modules owing to their high electrical conductivity and appreciable Seebeck coefficient, which facilitate the fabrication of flexible energy-harvesting devices. SWCNT were functionalized with an exfoliated MXene structure using noncovalent bonding, which enhanced their thermoelectric properties. MXene was combined with SWCNT via vacuum filtration to fabricate free-standing films with SWCNT contents ranging from 2 to 100 wt%. The resulting composite films exhibited p-type thermoelectric behavior. The composite containing 50 wt% SWCNT and 50 wt% MXene exhibited the highest Seebeck coefficient (35.26 µV K−1) and electrical conductivity (46 498 S m−1) with a power factor of 57.8 µW m−1 K−2. These values were higher than those of pure SWCNT, which showed a Seebeck coefficient of 28.93 µV K−1, a power factor of 27.1 µW m−1 K−2, and an electrical conductivity of 32 362 S m−1, respectively. The optimized 50 wt% SWCNT/MXene composition was subsequently used to form a polyurethane nanocomposite using a co-solvent technique. The disulfide chain-extended polyurethane served as the polymer matrix, promoting uniform dispersion of the fillers in the thermoelectric module. The fabricated module provided an average Seebeck coefficient of ∼197.49 µV K−1 over a temperature difference ranging from 24.30 to 47.50 K. The fabricated six-leg thermoelectric module generated a maximum power output of 0.95 µW. This modification is advantageous for flexible thermoelectric applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"34 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225829","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}

引用次数: 0

First-principles prediction of the thermoelectric properties of Sn(S0.2Se0.8) alloys Sn（S0.2Se0.8）合金热电性能的第一性原理预测

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-10-19 DOI: 10.1039/d6cp02931k

Min Zhang,Joseph Flitcroft,Jonathan Skelton

{"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}

引用次数: 0

Protein Adsorption and Drug Delivery Potential of Graphitic Carbon Nitride Nanorods: Physicochemical Insights with Human Serum Albumin and Quercetin 石墨氮化碳纳米棒的蛋白质吸附和药物传递潜力：与人血清白蛋白和槲皮素的物理化学见解

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-10-19 DOI: 10.1039/d6cp02919a

Catherine Pasangha,Nand Kishore

{"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}

引用次数: 0

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 通过NMR、CIDNP和分子动力学模拟研究了非甾体抗炎药s -酮洛芬与溶液中(L/D)-Trp-Leu-Pro-Phe肽光诱导相互作用的立体选择性

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-10-19 DOI: 10.1039/d6cp02914k

Olga Selyutina,Nikolay Polyakov,Alexander S Molokoedov,Maria V Sidorova,Dmitry Avdeev

{"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}

引用次数: 0

Probing Chiral Chromatography Systems in Vacuo: Cryogenic Ion Trap Laser Spectroscopy of Diastereomeric Copper(II)-Proline-Tyrosine Complexes. 探究真空中的手性色谱系统：非对映体铜(II)-脯氨酸-酪氨酸配合物的低温离子阱激光光谱。

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-10-19 DOI: 10.1039/d6cp03233h

Tomonori Izu,Kien Xuan Vo,Keisuke Hirata,Masaaki Fujii,Shun-ichi Ishiuchi,Anne Zehnacker

{"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}

引用次数: 0

Unveiling the excited-state cycloaddition mechanism of crystalline 9-anthracenecarboxylic acid via transient absorption spectroscopy and theoretical calculations 通过瞬态吸收光谱和理论计算揭示了结晶9-蒽甲酸的激发态环加成机理

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-10-19 DOI: 10.1039/d6cp03469a

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

{"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}

引用次数: 0

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 Janus BrClM （M = Ti, Zr, Hf）单层：带隙、表面偶极子和光响应的第一原理见解和限制域机器学习势分析

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-10-19 DOI: 10.1039/d6cp03121h

Babar Ali,Ahsan Javed,Muhammad Ali,Zijing Lin

{"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}

引用次数: 0