Structural Chemistry最新文献_第5页

Dissociation enthalpies of first and second row AO and OAO species: high level quantum chemical calculations 第一和第二行AO和OAO种的解离焓：高水平量子化学计算

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-08-23 DOI: 10.1007/s11224-025-02593-5

Nastasia Mauger, Kenneth D. Jordan, Joel F. Liebman

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Unveiling the resemblances in structures and electronic properties of Sin, GeSin–1, and Ge2Sin–2 clusters for n = 3–20 揭示了n = 3-20的Sin、GeSin-1和Ge2Sin-2簇在结构和电子性质上的相似性

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-08-20 DOI: 10.1007/s11224-025-02592-6

Feipeng Zhang, Rui Chen, Chaoyong Wang, Kai Wang

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Novel super hard orthorhombic and hexagonal C12 allotropes: crystal structure rationale and DFT investigations 新型超硬正交和六方C12同素异形体：晶体结构原理和DFT研究

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-08-20 DOI: 10.1007/s11224-025-02576-6

Samir F. Matar

{"title":"Novel super hard orthorhombic and hexagonal C12 allotropes: crystal structure rationale and DFT investigations","authors":"Samir F. Matar","doi":"10.1007/s11224-025-02576-6","DOIUrl":"10.1007/s11224-025-02576-6","url":null,"abstract":"<div>Novel orthorhombic and hexagonal C12 allotropes with respective topologies unj and umy were devised from crystal chemistry supported by subsequent density functional theory (DFT)-based calculations of ground state structures and energy-derived physical properties. Both allotropes were found with high density magnitude of 3.24 g/cm3 below diamond (3.55 g/cm3) and mechanically stable with large Vickers hardness magnitudes: HV(unj C12) = 72 GPa and HV(umy C12) = 45 GPa, letting consider them as ultrahard and superhard respectively. Being dynamically stable with positive phonon frequencies, the two allotropes show relationship trends with diamond experimental CV = f(T) heat capacity discreet values. The electronic band structures show insulating properties with large band gap like diamond for unj C12 and a smaller gap for semi-conducting umy-C12. A holistic interrelationship: “crystal structure ↔ mechanical ↔ dynamic ↔ electronic properties” is proposed.\u0000</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 2","pages":"767 - 774"},"PeriodicalIF":2.2,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388589","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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Sensing properties of novel β-arsenic antimonene nanosheets towards allethrin and permethrin vapours—a first-principles investigation 新型β-砷锑烯纳米片对丙烯菊酯和氯菊酯蒸汽的传感特性——第一性原理研究

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-08-18 DOI: 10.1007/s11224-025-02588-2

M. Vaishnavi, V. Nagarajan, R. Chandiramouli

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Two-dimensional crystallization of pentagonal symmetric molecules 五边形对称分子的二维结晶

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-08-18 DOI: 10.1007/s11224-025-02584-6

Karl-Heinz Ernst

{"title":"Two-dimensional crystallization of pentagonal symmetric molecules","authors":"Karl-Heinz Ernst","doi":"10.1007/s11224-025-02584-6","DOIUrl":"10.1007/s11224-025-02584-6","url":null,"abstract":"<div>Fivefold symmetry is incompatible with the translational periodicity of two-dimensional crystalline lattices. Nonetheless, aperiodic tilings, such as those introduced by Penrose and anticipated in Islamic geometric art, have demonstrated that local fivefold symmetry and long-range order can coexist without periodic repetition. Inspired by these mathematical constructs, recent advances in surface science have enabled the study of molecular self-assembly in two dimensions using molecules with intrinsic fivefold symmetry. In particular, penta-substituted derivatives of corannulene—rigid, bowl-shaped molecules resembling hard pentagons—exhibit intriguing self-assembly behavior on metal surfaces. Scanning tunneling microscopy (STM) reveals that these molecules organize into dense monolayers with stripe and rotator packing motifs reminiscent of theoretically predicted pentagonal tilings. Subtle variations in chirality and substitution patterns lead to diverse plane group symmetries (pm, p1, p2gg), domain boundaries, and packing densities. The balance between molecular geometry, chirality, and substrate interactions governs the emergence of ordered phases. These findings deepen our understanding of symmetry frustration, quasiperiodicity, and the transition between local and global order in molecular monolayers, with implications for the design of functional nanostructured materials.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 6","pages":"1973 - 1982"},"PeriodicalIF":2.2,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-025-02584-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666016","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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First-principles quantum investigations on rare-earth based pyrochlore oxides RE2Th2O7 (RE = Nd, Pr) for optoelectronics, thermoelectric, and spintronics applications 稀土基焦绿氧化物RE2Th2O7 （RE = Nd, Pr）光电子学、热电学和自旋电子学应用的第一线原理量子研究

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-08-18 DOI: 10.1007/s11224-025-02567-7

Zeesham Abbas, Amna Parveen, Imed Boukhris, Ali Akremi, V. K. Mishra

{"title":"First-principles quantum investigations on rare-earth based pyrochlore oxides RE2Th2O7 (RE = Nd, Pr) for optoelectronics, thermoelectric, and spintronics applications","authors":"Zeesham Abbas, Amna Parveen, Imed Boukhris, Ali Akremi, V. K. Mishra","doi":"10.1007/s11224-025-02567-7","DOIUrl":"10.1007/s11224-025-02567-7","url":null,"abstract":"<div>Pyrochlore oxides are progressively becoming potential candidates for thermoelectric power generation and solar energy owing to their unique electronic structures that are advantageous for optoelectronic and thermoelectric characteristics. The spintronic, optoelectronic and thermoelectric properties of novel pyrochlore oxides including RE2Th2O7 (RE = Nd, Pr) are analyzed to evaluate their potential for industrial applications. All Calculations are performed using ab-initio calculations based on density functional theory (DFT) approach. Nd2Th2O7 and Pr2Th2O7 are direct bandgap semiconductors with energy bandgaps of 2.88 and 2.79 eV, respectively, in both spin channels. Their paramagnetic behavior is analyzed, and magnetic moments can be deduced by examining band patterns perceived in energy band structures of RE2Th2O7 (RE = Nd, Pr) associated electronic states in spin up and spin down channels. Significant values of magnetic moments (({mu }_{B})) for Nd2Th2O7 and Pr2Th2O7 are 12.0 and 7.001, respectively. RE2Th2O7 (RE = Nd, Pr) show a significant absorption of incident photons in the near-UV constituency in both spin channels. The optical reflectivity spectra (R(omega )) for RE2Th2O7 (RE = Nd, Pr) exhibit a lower reflectance value of about 20% within presented energy range. The positive values of Seebeck coefficient ((S)) indicate p-type semiconducting behavior of RE2Th2O7 (RE = Nd, Pr). Nd₂Th₂O₇ is promising candidate for thermoelectric device applications as its ZT value is 0.99.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 5","pages":"1597 - 1614"},"PeriodicalIF":2.2,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145122117","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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Critical assessment of QTAIM descriptors of intermolecular interactions at the promolecular level 原分子水平上分子间相互作用QTAIM描述符的关键评估

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-08-13 DOI: 10.1007/s11224-025-02585-5

Alexey S. Romanenko, Ivan V. Ananyev

{"title":"Critical assessment of QTAIM descriptors of intermolecular interactions at the promolecular level","authors":"Alexey S. Romanenko, Ivan V. Ananyev","doi":"10.1007/s11224-025-02585-5","DOIUrl":"10.1007/s11224-025-02585-5","url":null,"abstract":"<div>Intermolecular interactions play a pivotal role in chemical processes such as catalysis, crystal formation, and drug-protein complexation. The Quantum Theory of Atoms in Molecules (QTAIM) provides a robust framework for analyzing these interactions through topological descriptors of electron density. However, the computational cost of obtaining accurate electron density distributions for large systems remains a challenge. This study critically evaluates the promolecular approximation (Independent Atom Model, IAM) as a cost-effective alternative for QTAIM analysis, focusing on its ability to describe various non-covalent interactions, including hydrogen bonds, halogen bonds, π…π stacking, and dispersion interactions. By comparing promolecular and density functional theory (DFT) results across diverse molecular systems, we demonstrate that the IAM model reliably reproduces trends in QTAIM descriptors, particularly for weaker and medium-strength interactions. However, in the case of some types of non-directional interactions, the molecular graph is often incorrectly predicted. Furthermore, we propose a semi-quantitative model to estimate intermolecular binding energies using promolecular-derived descriptors, showcasing the potential of IAM for large-scale applications in supramolecular chemistry and materials science.\u0000</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 5","pages":"1649 - 1666"},"PeriodicalIF":2.2,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145121893","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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Hydrogen storage using Li+ decorated bicyclo[2.2.1]hepta-2,5-diene molecule: A theoretical investigation Li+修饰双环[2.2.1]庚-2,5-二烯分子储氢的理论研究

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-08-13 DOI: 10.1007/s11224-025-02577-5

Tayebeh Konani, Abedien Zabardasti, Mohammad N. AL-Baiati

{"title":"Hydrogen storage using Li+ decorated bicyclo[2.2.1]hepta-2,5-diene molecule: A theoretical investigation","authors":"Tayebeh Konani, Abedien Zabardasti, Mohammad N. AL-Baiati","doi":"10.1007/s11224-025-02577-5","DOIUrl":"10.1007/s11224-025-02577-5","url":null,"abstract":"<div>Ab initio calculations were used to analyze triply interactions of bicycle [2.2.1] hepta-2,5-diene (BCH), Li+, and nH2 (n = 1–13) molecules at the MP2/6–311 + + G(d,p) computational level. The C = C double bonds at the BCH molecule have enough potential to get Li+ to absorb H2 molecules and form (BCH)Li(H2)n+ aggregates. Our results indicate that up to 4H2 molecules through Li-bonding can associate with Li+ on (BCH)Li+, the rest of H2 molecules by C-H…H2 dihydrogen bond or H2…H2 hydrogen bond interactions have been added to the (BCH)Li(H2)4+ to give greater (BCH)Li(H2)n+ complexes. Also, Li…H2 Li-bonding is stronger than C-H…H2, and H2…H2 is the weakest interaction in this series. The results show that the interaction energy of the H2 molecules on (BCH)Li(H2)n+ complexes decreases with increasing number of H2 molecules. The vibrational spectrum of the optimized (BCH)Li(H2)n+ complexes shows that stretching frequencies of C = C and H2 show redshifts and blue shifts with complex formation, respectively. The cooperativity in (BCH)Li(H2)n+ complexes has been evaluated. The structures of complexes have been analyzed using AIM and NBO methodologies.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 2","pages":"753 - 766"},"PeriodicalIF":2.2,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388588","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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Unraveling the impact of regioisomerism on the thermal stability of highly nitrated energetic pyrazoles: a DFT study 区域异构体对高硝化活性吡唑热稳定性的影响：一项DFT研究

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-08-12 DOI: 10.1007/s11224-025-02589-1

Zhihui Gu, Mengjie Bo, Zikai Gao, Congming Ma, Peng Ma

{"title":"Unraveling the impact of regioisomerism on the thermal stability of highly nitrated energetic pyrazoles: a DFT study","authors":"Zhihui Gu, Mengjie Bo, Zikai Gao, Congming Ma, Peng Ma","doi":"10.1007/s11224-025-02589-1","DOIUrl":"10.1007/s11224-025-02589-1","url":null,"abstract":"<div>Highly nitrated energetic materials exhibit excellent detonation performance but often suffer from high sensitivity. Regioisomerization is a widely used strategy to regulate their stability. In this study, density functional theory (DFT) calculations at the M06-2X/6-311G(d,p) and M06-2X/def2-TZVP levels were performed to investigate the effect of regioisomerism on the thermal decomposition behavior of three highly nitrated pyrazole-based energetic materials: 5-methyl-3,4-dinitro-1-(trinitromethyl)-1H-pyrazole (1), 4-methyl-3,5-dinitro-1-(trinitromethyl)-1H-pyrazole (2), and 3,5-bis-(dinitromethyl)-4-nitro-1H-pyrazole (3). The initial decomposition pathways were explored, with transition states validated via intrinsic reaction coordinate (IRC) calculations, and Gibbs free energy and wavefunction analyses conducted using Shermo and Multiwfn. The results show that nitro dissociation and hydrogen transfer are the dominant decomposition pathways for compounds 1 and 2, respectively, consistent with their decomposition temperatures. For compound 3, which decomposes in hydrated crystalline form, an implicit water model was used to simulate the solvent effect. Although not associated with the lowest energy barrier, the hydrogen transfer to a neighboring nitrogen atom features a relatively favorable barrier (41.1 kcal/mol) and substantial exothermicity, making it the most likely initial decomposition pathway for compound 3 and consistent with its observed low thermal stability. Frontier orbital analysis indicated stable LUMO distributions and moderate ΔE changes for compounds 1 and 2 during isomerization. These findings provide insight into how regioisomerism and solvent effects influence the thermal stability of energetic materials.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 2","pages":"741 - 751"},"PeriodicalIF":2.2,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388575","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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Gauche and trans ethylenediammonium in the structures of ethylenediammonium tetrafluoroborate and tetrafluoroborate-fluoride crystals 四氟硼酸乙二铵和四氟硼酸-氟晶体结构中的间扭式和反式乙二铵

IF 2.2 4区化学

Structural Chemistry Pub Date : 2025-08-12 DOI: 10.1007/s11224-025-02579-3

Andrii Vakulka, Evgeny Goreshnik

{"title":"Gauche and trans ethylenediammonium in the structures of ethylenediammonium tetrafluoroborate and tetrafluoroborate-fluoride crystals","authors":"Andrii Vakulka, Evgeny Goreshnik","doi":"10.1007/s11224-025-02579-3","DOIUrl":"10.1007/s11224-025-02579-3","url":null,"abstract":"<div>The possible stereochemical conformations of the isolated ethylenediammonium dication were discussed, along with an assessment of their relative stabilities. Crystals of ethylenediammonium tetrafluoroborate-fluoride and tetrafluoroborate salts were prepared and structurally characterised. The crystal packing and hydrogen bonding interactions involving the ethylenediammonium dication were also described and analysed. In the structure of [enH2](BF4)F, the ethylenediammonium dication adopts a superposition of left-handed and right-handed C2-symmetrical gauche (synclinal) conformations, with an NCCN torsion angle of ± 75.49(10)°. These conformers form a cyclic ({text{R}}_{2}^{1}(7)) [enH2]F+ fragment through hydrogen bonding with the fluoride anion. Three such ({text{R}}_{2}^{1}(7)) [enH2]F+ fragments, along with a fluoride anion from a fourth [enH2]F+ unit, associate into a more complex ({text{R}}_{8}^{4}(16)) ring motif within the hydrogen-bonded network of [enH2](BF4)F. In the [enH2](BF4)2 salt, the ethylenediammonium dications adopt a trans configuration, corresponding to C2h point group symmetry. Raman and IR spectra were recorded and tentatively interpreted. A clear spectroscopic distinction between the trans and gauche conformations of the ({mathbf{e}mathbf{n}text{H}}_{2}^{2+}) dication was observed and discussed.</div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 1","pages":"81 - 100"},"PeriodicalIF":2.2,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-025-02579-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043451","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0