Chemphyschem最新文献_第3页

Low-cost periodic calculations of metal-organic frameworks: A GFN1-xTB perspective. 金属有机框架的低成本周期性计算：GFN1-xTB视角。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-05-05 DOI: 10.1002/cphc.202500081

Mateusz Pokora, Jakub Goclon, Johannes Margraf, Chiara Panosetti, Artem Samtsevych, Piotr Paneth

{"title":"Low-cost periodic calculations of metal-organic frameworks: A GFN1-xTB perspective.","authors":"Mateusz Pokora, Jakub Goclon, Johannes Margraf, Chiara Panosetti, Artem Samtsevych, Piotr Paneth","doi":"10.1002/cphc.202500081","DOIUrl":"https://doi.org/10.1002/cphc.202500081","url":null,"abstract":"Semiempirical extended tight-binding (GFN1-xTB) and semilocal DFT(PBE+D3) calculations were performed to evaluate the structural and electronic properties of five metal-organic frameworks (MOFs): rigid MOF-5(Zn), IRMOF(II)-74(Mg), ZIF-8(Zn); and flexible MIL-53(Al) and MIL-53(Fe). It was found that GFN1-xTB exhibits a similar performance to that of DFT in terms of accuracy of lattice vector preservation. Structural integrity is further supported by the low average RMSD of the atomic positions, which remains below 0.3 A. Consequently, the textural properties are also well preserved by GFN1-xTB, showing good agreement with those obtained from DFT. GFN1-xTB molecular dynamics (MD) simulations exhibit structural stability and correctly predict structural responses to temperature, which is fully consistent with experimental results. In addition, based on MD trajectories, we constructed time-averaged X-ray diffraction patterns that closely aligned with experimental data. More importantly, GFN1-xTB performed exceptionally well at predicting the band gap. Overall, GFN1-xTB offers almost semilocal DFT accuracy with significantly higher computational efficiency, making it a valuable tool for describing the geometric, textural, dynamic, and selected electronic properties of MOFs.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500081"},"PeriodicalIF":2.3,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143992469","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

Diels-Alder Reaction of C60 and C70 Fullerenes Confined in a Nanohoop: A Theoretical Study. 纳米环内C60和C70富勒烯diols - alder反应的理论研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-05-04 DOI: 10.1002/cphc.202401026

Chun-Xiang Li, Jun-Ru He, Yu-Ping Zhang, Ling-Bo Qu, Long-Pan Feng, Jia-Li Peng, Chengxing Cui

{"title":"Diels-Alder Reaction of C60 and C70 Fullerenes Confined in a Nanohoop: A Theoretical Study.","authors":"Chun-Xiang Li, Jun-Ru He, Yu-Ping Zhang, Ling-Bo Qu, Long-Pan Feng, Jia-Li Peng, Chengxing Cui","doi":"10.1002/cphc.202401026","DOIUrl":"https://doi.org/10.1002/cphc.202401026","url":null,"abstract":"The reactivity of the bonds in fullerenes plays an important role in the chemical modification of their structures. It has been proved that fullerenes can be included as a guest molecule in the conjugated [n]cyclodibenzopentalene nanohoop to form intriguing host-guest systems with potential organic material applications. Experimental results show that the strength of the interaction between fullerenes and [n]cyclodibenzopentalenes is very high. Here, we theoretically investigated the effect of encapsulating C60 and C70 fullerenes in the [4]cyclodibenzopentalene nanohoop on the reactivity of the bonds in C60 and C70. The calculated results indicate that the binding energy between the nanohoop and C60 is 2.7 kcal mol-1 higher than that between the nanohoop and C70. Compared with the isolated fullerenes, the differences between the reactivities of the bonds in C60 and C70 enclosed in the nanohoop are smaller because of their interaction with the nanohoop. The distortion/interaction model was used to analyze the underlying reasons. We believe that the results of this study will aid in the research fields of supramolecular chemistry and fullerene chemistry.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401026"},"PeriodicalIF":2.3,"publicationDate":"2025-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143961367","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

Molecular Simulation Insights into Acid Gas Interactions within Ni-based Fluorinated Square-Pillared MOF. 分子模拟洞察酸性气体相互作用在ni基氟化方柱MOF。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-05-03 DOI: 10.1002/cphc.202500040

Silda Peters, Renjith S Pillai, Anantharaj Sengeni, Tumpa Sadhukhan

{"title":"Molecular Simulation Insights into Acid Gas Interactions within Ni-based Fluorinated Square-Pillared MOF.","authors":"Silda Peters, Renjith S Pillai, Anantharaj Sengeni, Tumpa Sadhukhan","doi":"10.1002/cphc.202500040","DOIUrl":"https://doi.org/10.1002/cphc.202500040","url":null,"abstract":"The increasing prominence of metal-organic frameworks (MOFs) in gas separation technologies has sparked significant interest in their application in flue gas treatment. Nevertheless, the adsorption of acidic gases in MOFs presents significant challenges owing to their complex interactions with the framework. Our research explored the adsorption interactions of acidic gases and their mixtures with [Ni(1,4-pyrazine)₂(AlF₅)]ₙ (ALFFIVE-Ni-Pyr) while considering the flexibility of the framework. Using grand canonical Monte Carlo (GCMC) simulations, we evaluated guest-host interactions, focusing on gas loading, whereas molecular dynamics (MD) simulations highlighted the structural dynamics induced by guest molecules within the framework. Density Functional Theory (DFT) calculations further confirmed the interactions between acidic gases and the framework. Our results show a significantly higher adsorption capacity for SO₂ than for CO₂ and NO₂, particularly in gas mixtures, highlighting the adaptability of the framework and its superior performance for acidic gas separation. This study aims to contribute to advancements in gas separation processes and provide valuable insights into the optimization of MOFs for industrial applications.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500040"},"PeriodicalIF":2.3,"publicationDate":"2025-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143962865","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

Molecular Fragmentation as a Strategy to Access Hyperpolarised Compounds from Para-Hydrogen. 分子断裂作为从对氢中获取超极化化合物的策略。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-05-01 DOI: 10.1002/cphc.202500105

Philip L Norcott

引用次数: 0

The importance of solvent adsorption in liquid phase reaction kinetics: Nitrobenzene hydrogenation in Pd (111) as a case study. 溶剂吸附在液相反应动力学中的重要性：以Pd（111）中硝基苯加氢为例。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-29 DOI: 10.1002/cphc.202500110

Javiera Herrera, Pablo Gamallo, Cristian H Campos, Gerard Alonso

{"title":"The importance of solvent adsorption in liquid phase reaction kinetics: Nitrobenzene hydrogenation in Pd (111) as a case study.","authors":"Javiera Herrera, Pablo Gamallo, Cristian H Campos, Gerard Alonso","doi":"10.1002/cphc.202500110","DOIUrl":"https://doi.org/10.1002/cphc.202500110","url":null,"abstract":"The catalytic hydrogenation of Nitrobenzene is an essential reaction to produce Aniline. This reaction can be catalyzed with noble metal-based catalysts such as Pd. In fact, hydrogenation takes place at room temperature in solution, where Nitrobenzene is consecutively hydrogenated until reaching Aniline. It has been empirically proven that the selection of the solvent affects the catalytic activity and selectivity of this reaction towards Aniline. However, there is not a complete theoretical study that clarifies the role of solvents and their impact on the reaction mechanism. In this contribution we have carried out a combined density functional theory (DFT) and experimental evaluation of the Nitrobenzene hydrogenation to Aniline under three different solvents (i.e., the non-polar cyclohexane, the polar aprotic ethyl acetate, and the polar protic water). Experimentally, we have carried out the reaction with a commercial catalyst 5% Pd/C, which was modeled in DFT with a Pd (111) surface under an implicit solvation model. The results reveal that less polar solvents compete for the catalyst adsorption sites with the reactants, producing longer induction times. On the other hand, the solvent has little effect on the reaction rate, but it does determine the pathway.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500110"},"PeriodicalIF":2.3,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143968619","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

Millisecond phase transition kinetics of lyotropic liquid crystalline nanoparticles observed by time-resolved small angle x-ray solution scattering. 时间分辨小角x射线溶液散射观察溶致液晶纳米颗粒的毫秒相变动力学。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-28 DOI: 10.1002/cphc.202401072

Changmin Lee, Arnold M Chan, Adam K Nijhawan, Madeline B Ho, Irina Kosheleva, Lin X Chen

{"title":"Millisecond phase transition kinetics of lyotropic liquid crystalline nanoparticles observed by time-resolved small angle x-ray solution scattering.","authors":"Changmin Lee, Arnold M Chan, Adam K Nijhawan, Madeline B Ho, Irina Kosheleva, Lin X Chen","doi":"10.1002/cphc.202401072","DOIUrl":"https://doi.org/10.1002/cphc.202401072","url":null,"abstract":"This study investigates the dynamic behavior of lyotropic liquid crystal nanoparticles (LCNPs), which are widely recognized for their applications in drug delivery. By employing nanosecond near-infrared (NIR) laser pulse-induced temperature jump (T-jump) and time-resolved X-ray solution scattering (TRXSS), the structural dynamics of phase transitions in phytantriol-based cubosomes and hexosomes are revealed. Both cubosome and hexosome LCNPs undergo phase transitions into non-crystalline phases at high temperatures. Their phase transition kinetics, occurring within milliseconds (ms) and involving one intermediate structure, were captured. Additionally, the reverse self-assembly processes of LCNPs were observed, occurring on the timescale of a few hundred ms. To our knowledge, this is the first observation of LCNP T-jump induced phase transitions on the ms timescale and their reverse self-assembly. These findings provide valuable insights into the LCNP phase transition processes, with potential implications for drug delivery applications.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401072"},"PeriodicalIF":2.3,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143983809","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

CPL Signal Inversion in Aza-[7]Helicene Derivatives: Theoretical Insight into Pyridine Nitrogen Position and Protonation Effects. Aza-[7]螺旋烯衍生物的CPL信号反转：对吡啶氮位置和质子化效应的理论见解。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-27 DOI: 10.1002/cphc.202500106

Ran Wei, Jia Tang, Yan Liu, Hang Su, Hua Wang, Zhiying Ma, Zhitao Shen

{"title":"CPL Signal Inversion in Aza-[7]Helicene Derivatives: Theoretical Insight into Pyridine Nitrogen Position and Protonation Effects.","authors":"Ran Wei, Jia Tang, Yan Liu, Hang Su, Hua Wang, Zhiying Ma, Zhitao Shen","doi":"10.1002/cphc.202500106","DOIUrl":"https://doi.org/10.1002/cphc.202500106","url":null,"abstract":"Designing molecules that can produce controllable circularly polarized luminescence (CPL) and achieve CPL signal inversion is challenge. While CPL switches can be achieved by modifying chiral molecules' structures or using external stimuli (e.g., concentration, temperature, solvent, pH), a quantitative framework for modulating CPL signals, especially for inversion, remains absent. In this study, we presented a theoretical approach combining density functional theory (DFT), time-dependent DFT, and thermal vibration correlation function theory to investigate the effects of pyridine nitrogen positions and protonation on the CPL performance of the aza-[7]helicene skeleton. Our findings show that protonation markedly narrows the HOMO-LUMO gap, enhancing electronic properties and optoelectronic potential. It also induces redshifts in fluorescence and CPL signal reversals, modulating optical properties and decay pathways. The HOMO-LUMO transition is the main driver of spectral changes, with charge separation in protonated forms due to the pyridine group's electron-withdrawing effect. The position of pyridine nitrogen and protonation state influence chiroptical parameters, altering CPL signals without changing molecular configurations, thus impacting optoelectronic applications. This study offers insights into the structure-property relationship of aza-[7]helicenes derivatives and their protonated forms, guiding the rational design of helicenes featuring pH-triggered CPL switches, controllable CPL signals, and superior optoelectronics properties.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500106"},"PeriodicalIF":2.3,"publicationDate":"2025-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143955592","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

Magnetization and Polarization of Coupled Nuclear Spins Ensembles at High Magnetic Fields. 高磁场下耦合核自旋系综的磁化和极化。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-23 DOI: 10.1002/cphc.202500092

Danila A Barskiy, Andrey Pravdivtsev

{"title":"Magnetization and Polarization of Coupled Nuclear Spins Ensembles at High Magnetic Fields.","authors":"Danila A Barskiy, Andrey Pravdivtsev","doi":"10.1002/cphc.202500092","DOIUrl":"https://doi.org/10.1002/cphc.202500092","url":null,"abstract":"In nuclear magnetic resonance (NMR), the bulk magnetization of a sample is commonly assumed to be proportional to spin polarization, with each spin of the same type contributing equally to the measured signal. In this work, we prove the high-field theorem for general spin-I systems (where I is the spin quantum number): the total measurable NMR signal remains unaffected by the grouping of spins into equivalent units (e.g., molecules), provided the system is at thermodynamic equilibrium in the high field limit ([[EQUATION]], where [[EQUATION]] is the Larmor frequency and [[EQUATION]] characterizes internal spin-spin interactions). The results are derived using both magnetization equations and density matrix formalism. The theorem, however, does not extend to conditions far from thermodynamic equilibrium (e.g., hyperpolarization), NMR of solids in the regime when quadrupolar or dipole-dipole interactions are not negligible, and zero- to ultralow-field NMR. We also present three educational problems designed to deepen understanding of the material in classroom settings. This work reinforces established principles in magnetic resonance but also highlights areas for further exploration.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500092"},"PeriodicalIF":2.3,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143987214","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

Vibrational Partition Functions from Bond Order and Populations Relationships. 键序与居群关系中的振动配分函数。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-22 DOI: 10.1002/cphc.202500085

Barbaro Zulueta, John A Keith

引用次数: 0

Flexible 2D structure formation of [C1C1Im][Tf2N] on Ag(111). [C1C1Im][Tf2N]在Ag（111）上形成柔性二维结构。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-22 DOI: 10.1002/cphc.202500163

Afra Gezmis, Timo Talwar, Manuel Meusel, Andreas Bayer, Florian Maier, Hans-Peter Steinrück

{"title":"Flexible 2D structure formation of [C1C1Im][Tf2N] on Ag(111).","authors":"Afra Gezmis, Timo Talwar, Manuel Meusel, Andreas Bayer, Florian Maier, Hans-Peter Steinrück","doi":"10.1002/cphc.202500163","DOIUrl":"https://doi.org/10.1002/cphc.202500163","url":null,"abstract":"We studied the first layer of the ionic liquid (IL) 1-3-dimethylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C1C1Im][Tf2N]) on Ag(111) under ultrahigh vacuum conditions using scanning-tunneling and atomic-force microscopy, and compare the observed results to the behavior found on Au(111), Cu(111) and Pt(111). On Ag(111), we observe two stable phases, a stripe phase and a hexagonal phase. The hexagonal phases on Ag(111), Au(111) and Pt(111) exhibit a similar, checkerboard-like structure with surface areas per ion pair ranging from 0.77 to 0.85 nm2. In contrast, the striped phases behave differently: While for Au(111) and Cu(111) we observe similar surface areas per ion pair as for the hexagonal phases, for Ag(111) the area per ion pair varies from 0.50 to 1.14 nm2. This broad range results from a large variation of next neighbor intra- and inter-row distances. We attribute these very substantial differences to the specific interplay of lateral interactions within IL rows and the vertical interaction with the substrate. The pronounced polymorphism observed for [C1C1Im][Tf2N] on Ag(111) suggests that this system represents a special case, with the weakest adsorbate/substrate interaction among the studied systems, due to the absence of covalent interactions as compared to Cu(111), and only moderate van der Waals interactions as compared to Au(111).","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500163"},"PeriodicalIF":2.3,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143978525","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