Physical Chemistry Chemical Physics最新文献_第2页

Stacking-Controlled Magnetic Anisotropy Switching in bilayer Janus Mn2Cl3Br3 双层Janus Mn2Cl3Br3的堆叠控制磁各向异性开关

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-29 DOI: 10.1039/d5cp01516b

Yanle Liang, Heng Gao, Hui Zhang, Musen Li, Chang Liu, Zhaohe Gao, Cheng Tang, Wei Ren

{"title":"Stacking-Controlled Magnetic Anisotropy Switching in bilayer Janus Mn2Cl3Br3","authors":"Yanle Liang, Heng Gao, Hui Zhang, Musen Li, Chang Liu, Zhaohe Gao, Cheng Tang, Wei Ren","doi":"10.1039/d5cp01516b","DOIUrl":"https://doi.org/10.1039/d5cp01516b","url":null,"abstract":"Bilayer Janus Mn2Cl3Br3 exhibit intriguing tunable magnetic anisotropy energy (MAE), governed by stacking configurations and halogen-specific orbital interaction. By density functional theory (DFT), we find that AA stacking in Mn2Cl3Br3 induces the MAE transition from in-plane to out-of-plane orientation, absent in bilayer Mn2Br3I3 and Mn2Cl3I3. This switching is driven by compressed Mn-Br interlayer distance that amplifies the positive contribution of MAE between px and py of Br while suppressing the pz-py contributions. In contrast, bilayer Janus Mn2Br3I3 and Mn2Cl3I3 remain in-plane MAE due to the negative contribution of the pz-py interactionof I atoms. Stacking-dependent magnetic exchange interactions further modulate MAE in bilayer Janus Mn2Cl3Br3 with AA stacking exhibiting enhanced vertical magnetic exchange anisotropy critical for MAE switching. In contrast, AB stacking preserves in-plane MAE due to suppressed magnetic interlayer coupling. The interplay of halogen orbital engineering and stacking orders offers a versatile pathway to tune the magnetic anisotropy in van der Waals magnets for designing 2D spintronic materials.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"160 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165255","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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Full-dimensional neural network potential energy surface for the multi-channel photodissociation of HNSiO via its S1 band 利用HNSiO的S1波段进行多通道光解的全维神经网络势能面

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-29 DOI: 10.1039/d5cp00818b

Tingchuan Shang, Siting Hou, Huixian Han, Changjian Xie

{"title":"Full-dimensional neural network potential energy surface for the multi-channel photodissociation of HNSiO via its S1 band","authors":"Tingchuan Shang, Siting Hou, Huixian Han, Changjian Xie","doi":"10.1039/d5cp00818b","DOIUrl":"https://doi.org/10.1039/d5cp00818b","url":null,"abstract":"A full-dimensional potential energy surface (PES) for the first excited state S1(1A″) of HNSiO has been built up by the neural network method based on more than 91000 ab initio points, covering six possible product channels for the photodissociation reactions: HNSiO + hv → H(2S) + NSiO(2Π) / HN(1Δ) +SiO(1Σ+) / HNSi(3Π) + O(3P) / NSi(2Σ) + OH(2Π) / N(2D) + SiOH(2Aʹ) / HSi(2Σ) + NO(2Π). Seventeen stationary points consisting of five local minima and twelve transition states were found on the S1 PES along the six dissociation pathways. Based on the newly constructed S1 PES, the quasi-classical trajectory calculations were carried out to study the photodissociation dynamics of HNSiO(S1) at the total energy ranging from 5.5 to 7.7 eV. It was found that although six product channels are energetically available at high total energies, the dominant (>90%) products are HN + SiO and H + NSiO. At low total energies the major product is HN + SiO, while for the total energy larger than 7.1 eV, the product channel H + NSiO becomes increasingly favored, due to the faster movement of the light H atom. This scenario is quite analogous to the photodissociation of HNCO in the S1 band. In particular, a high proportion of trajectories undergo the isomerization during the dissociation because of relatively low barriers separating the isomers. Due to the much shallower HOSiN and NSiOH wells compared to the HNSiO wells on the S1 PES, the transferred H atom after the isomerization returns to the HNSiO wells or dissociates directly, which leads to quite small percentages of other products N + SiOH, NSi + OH, and HSi + NO.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165248","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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Probing ultrafast heat transfer mechanisms in plasmonic gold nanostructures: FEM analysis of core–shell configurations under femtosecond laser irradiation 探测等离子体金纳米结构中的超快传热机制：飞秒激光辐照下核壳组态的有限元分析

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-29 DOI: 10.1039/d5cp00715a

Joshua Fernandes, Myoung-Jin Kim

{"title":"Probing ultrafast heat transfer mechanisms in plasmonic gold nanostructures: FEM analysis of core–shell configurations under femtosecond laser irradiation","authors":"Joshua Fernandes, Myoung-Jin Kim","doi":"10.1039/d5cp00715a","DOIUrl":"https://doi.org/10.1039/d5cp00715a","url":null,"abstract":"This study presents a comprehensive numerical investigation of the photothermal response of core–shell gold nanoshell (CGNS) and gold nanorod (CGNR) under femtosecond (fs) laser pulse irradiation. Using the two-temperature model (TTM) integrated with finite element modeling in COMSOL Multiphysics, we simulated the optical and thermal dynamics of these nanostructures. A key innovation in our approach is incorporating the temperature dependencies of electron heat capacity and electron–phonon coupling, allowing us to capture the non-linear thermal response at elevated electron temperatures. Our analysis showed that, while lattice temperatures increased linearly with laser fluence, electron temperatures exhibited a more complex non-linear trend, emphasizing the need for advanced modeling in high-fluence regimes. We evaluated how variations in key parameters, including aspect ratio, shell thickness, pulse duration, and refractive index, influence the optical and thermal properties of the nanostructures. Results revealed that CGNRs with higher aspect ratios exhibited significant red-shifts into the near-infrared (NIR) region, making them ideal for deep-tissue imaging and photothermal therapy (PTT), while thicker CGNS nanostructures demonstrated blue-shifts with reduced energy absorption. Shorter pulse durations led to higher peak electron temperatures, with CGNRs displaying faster heat dissipation than CGNS due to their elongated geometry. Furthermore, CGNRs demonstrated enhanced sensitivity to changes in the refractive index of the surrounding medium, making them particularly suited for sensing applications in the NIR-II region. This study provides key insights into optimizing core–shell nanostructures for advanced PTT and sensing technologies, laying the groundwork for the development of tailored nanomaterials for biomedical applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"58 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165250","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

DFT and SISSO Studies on the CO2 cycloaddition reaction to ethylene oxide catalyzed by intraframework M(II)-BEA zeolites 框架内M(II)-BEA分子筛催化CO2环加成反应生成环氧乙烷的DFT和SISSO研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-29 DOI: 10.1039/d5cp01341k

Winyoo Sangthong, Jakkapan Sirijaraensre

{"title":"DFT and SISSO Studies on the CO2 cycloaddition reaction to ethylene oxide catalyzed by intraframework M(II)-BEA zeolites","authors":"Winyoo Sangthong, Jakkapan Sirijaraensre","doi":"10.1039/d5cp01341k","DOIUrl":"https://doi.org/10.1039/d5cp01341k","url":null,"abstract":"The CO₂ cycloaddition with EO over M(II)-intraframework BEA zeolites, with and without TMAI as a co-catalyst is investigated using the M06-L functional. Without a co-catalyst, the catalytic process occurs through a concerted mechanism. The activation energy is calculated to be 39.9, 38.9, 38.6, and 39.6 kcal mol⁻¹ for M-DeAlBEA zeolites (M=Ni, Cu, Zn, and Mg), respectively. In the presence of the co-catalyst, the catalytic process proceeds through three consecutive steps: ring opening, CO₂ activation, and ring closure, with the latter being the rate-determining step (RDS) of the reaction. The incorporation of TMAI plays a crucial role in activating EO and CO₂, leading to a more kinetically favorable formation of ethylene carbonate compared to the concerted pathway. From the energy span model, the activation energies of the RDS for the stepwise CO₂ cycloaddition are 16.8, 24.7, 14.7, and 14.1 kcal mol⁻¹, respectively. The SISSO algorithm has been employed to develop a mathematical expression for predicting the higher activation energy required for EC production via two pathways. The highest activation energy for CO₂ cycloaddition can be approximated using the molecular orbital (MO) energies of the zeolite and co-catalyst, along with the EO and CO₂ adsorption free energies. The SISSO-derived activation energies closely match the DFT-calculated values, achieving an R² value of 0.998 and an RMSE of 1.52 kcal mol⁻¹.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"49 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165249","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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Outstanding Reviewers for Physical Chemistry Chemical Physics in 2024 2024年物理化学化学优秀审稿人

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-29 DOI: 10.1039/d5cp90098k

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Computational screening of transition-metal atom embedding in 1T-TaS2 monolayer defects as efficient oxygen-reduction/evolution-reaction bifunctional catalysts 过渡金属原子嵌入1T-TaS2单层缺陷作为高效氧还原/演化反应双功能催化剂的计算筛选

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-29 DOI: 10.1039/d5cp00809c

Junkai Xu, Rongxing Zhang, Yu Wu, Tongmeng Xing, Jianjun Fang, Jing Li, Xianfang Yue, Antonio J. C. Varandas

{"title":"Computational screening of transition-metal atom embedding in 1T-TaS2 monolayer defects as efficient oxygen-reduction/evolution-reaction bifunctional catalysts","authors":"Junkai Xu, Rongxing Zhang, Yu Wu, Tongmeng Xing, Jianjun Fang, Jing Li, Xianfang Yue, Antonio J. C. Varandas","doi":"10.1039/d5cp00809c","DOIUrl":"https://doi.org/10.1039/d5cp00809c","url":null,"abstract":"With the rapid development of global green energy and low-carbon economy, the development of high-performance, low-cost and stable catalysts for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is becoming more and more important. Herein, based on comprehensive density functional theory (DFT) computations, we explore the catalytic activity of metal-atom doped 1T-TaS2 single-atom catalysts (SACs) TM@1T-TaS2 for ORR and OER, where TM = V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au. It is found that Pd@1T-TaS2 can be an excellent bifunctional electrocatalyst with OER and ORR overpotentials (0.47 V/0.49 V) comparable to the noble metal catalysts. In view of the good catalytic activity of Pd@1T-TaS2 , the 4-electron process stepwise hydrogenation reaction energy barrier was further calculated with a maximum barrier of 0.44 eV. Additionally, it has been elucidated through volcano curves evolved from the scaling relation of adsorption energy that the good catalytic activity stems from the moderate adsorption of oxygenated intermediates. Finally, d-band center and crystal orbital Hamiltonian populations methods were used to explain the catalytic origin. Suitable d-band centers lead to moderate adsorption strength, further implying good catalytic performances.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"8 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165251","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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An embedding scheme for constraint-based orbital-optimized excitations in molecular and bulk environments 分子和体环境中基于约束的轨道优化激励嵌入方案

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-29 DOI: 10.1039/d5cp00839e

Yannick Lemke, Jörg Kussmann, Christian Ochsenfeld

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First principles prediction of wavelength-dependent isomerization quantum yields of a second-generation molecular nanomotor 第二代分子纳米马达波长相关异构化量子产率的第一性原理预测

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-28 DOI: 10.1039/d5cp01063b

Jesús Lucia-Tamudo, Michelle Menkel-Lantz, Enrico Tapavicza

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Aggregation-Induced Emission Mechanism of Styrene Derivative: A Theoretical Study 苯乙烯衍生物聚集致发射机理的理论研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-28 DOI: 10.1039/d4cp04742g

Aarzoo Aarzoo, Kenichiro Saita, Masato Kobayashi, Takao Tsuneda, Tetsuya Taketsugu, Ram KINKAR ROY

{"title":"Aggregation-Induced Emission Mechanism of Styrene Derivative: A Theoretical Study","authors":"Aarzoo Aarzoo, Kenichiro Saita, Masato Kobayashi, Takao Tsuneda, Tetsuya Taketsugu, Ram KINKAR ROY","doi":"10.1039/d4cp04742g","DOIUrl":"https://doi.org/10.1039/d4cp04742g","url":null,"abstract":"The aggregation-induced emission (AIE) mechanism of the fluorescent styrene derivative 4-dimethylamino-2-benzylidene malonic acid dimethyl ester (BIM) in methanol solution is theoretically investigated using spin-flip long-range corrected time-dependent density functional theory (SF-LC-TDDFT). The potential energy surfaces (PESs) for the ground (S0) and first singlet excited (S1) states of BIM were calculated along the rotation of the aryl main axis (α angle rotation), consistent with experimental observations. For the monomer, our findings reveal a significant reduction in oscillator strength, approaching zero at the optimized geometry in the S1 state. As this state corresponds to a charge transfer state, it suggests that the BIM monomer operates as a twisted intramolecular charge transfer (TICT) system, undergoing quenching through α angle rotation. The restriction of TICT, and consequently the inhibition of fluorescence quenching in the aggregate state, is also investigated by extracting the coordinates of 13 monomers from the crystal structure of BIM. The α-torsional angle of the central monomer was manually rotated in both clockwise and anti-clockwise directions to assess the intramolecular restrictions within the constrained environment. This analysis reveals that even a 10° rotation of the α-torsional angle, in either direction, causes the atoms of the central monomer to come into close contact with the atoms of the neighboring monomers. These short contacts effectively inhibit the TICT process, thereby leading to aggregation-induced emission.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"5 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153829","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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Correlations of surface tension for mixtures of n-alkanes as a function of the composition: applicability and performance analysis of existing models. 正构烷烃混合物表面张力随组成的相关性：现有模型的适用性和性能分析。

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-05-28 DOI: 10.1039/d5cp01354b

Angel Mulero, Ariel Hernández, Virginia Vadillo-Rodríguez, Isidro Cachadiña

{"title":"Correlations of surface tension for mixtures of n-alkanes as a function of the composition: applicability and performance analysis of existing models.","authors":"Angel Mulero, Ariel Hernández, Virginia Vadillo-Rodríguez, Isidro Cachadiña","doi":"10.1039/d5cp01354b","DOIUrl":"https://doi.org/10.1039/d5cp01354b","url":null,"abstract":"In this work, a large data set of experimental values of surface tension for binary mixtures of two n-alkanes have been compiled. These values are later fitted to different models of correlation as functions of molar fraction at various temperatures. All of these models use the surface tension of pure fluids as input data and may require between one and three adjustable coefficients. For some mixtures and/or temperatures, where the surface tension values of pure fluids have not been measured, predictions from previously proposed specific correlations for pure fluids are considered as an alternative. Different cases are studied accordingly with the availability of surface tension values for pure fluids: (i) available for both pure fluids, (ii) available for only one of the fluids, and (iii) unavailable for both fluids. Moreover, a fourth case is considered to include those mixtures and temperatures at which one of the fluids is supercritical. The applicability and accuracy of 10 different analytical correlation models are evaluated based on the percentage deviations between experimental and calculated values. Additionally, the Akaike Information Criterion is applied to identify the most suitable models. As a main result, it is found that predicted values from correlations for pure fluids can be used instead of experimental data without significantly affecting the accuracy and applicability of the models. Moreover, it is shown that the Winterfeld-Scriven-Davis model, which has a certain physicochemical basis and only one adjustable coefficient, provides the best overall results. However, this model cannot be applied when one of the fluids is supercritical and its surface tension is assumed to be zero. In this case, the Redlich-Kister correlation, with two or three adjustable coefficients, provides better results. More recent or more complex models are not necessary to achieve excellent accuracy for n-alkane mixtures and therefore should be avoided.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"57 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153827","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