Physical Chemistry Chemical Physics最新文献_第3页

Shear-dependent slip of an amphiphilic -hexanol self-assembled monolayer in a calcite nanopore 方解石纳米孔中两亲己醇自组装单层的剪切依赖滑移

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-11-09 DOI: 10.1039/d6cp02663j

Mohammad Mehdi Koleini,Mohammad Hasan Badizad

{"title":"Shear-dependent slip of an amphiphilic -hexanol self-assembled monolayer in a calcite nanopore","authors":"Mohammad Mehdi Koleini,Mohammad Hasan Badizad","doi":"10.1039/d6cp02663j","DOIUrl":"https://doi.org/10.1039/d6cp02663j","url":null,"abstract":"Amphiphilic molecules at solid–liquid interfaces can substantially modify molecular transport under nanoscale confinement, yet the coupling between the self-assembled monolayer (SAM) structure and flow remains poorly understood. Here, molecular dynamics simulations are used to investigate n-hexanol confined between calcite surfaces and to determine how its interfacial self-assembly influences pressure-driven transport. n-Hexanol spontaneously forms densely packed SAMs through strong interactions between hydroxyl headgroups and the calcite surface, producing a hydrophobic methyl-terminated interface. The SAM remains anchored under flow, while its molecular orientation becomes progressively broader with increasing driving force. Most notably, the slip length exhibits a non-monotonic dependence on the shear rate: it initially increases with shear rate and subsequently decreases at higher shear rates. We interpret this behavior as a competition between low interfacial friction associated with an ordered SAM and enhanced momentum dissipation associated with shear-induced conformational disorder and tail reorientation. Thus, the SAM acts not as a passive hydrophobic coating but as a shear-responsive molecular boundary layer. In-plane molecular diffusion remains Fickian, whereas motion normal to the surfaces is strongly restricted and becomes sub-diffusive as a consequence of confinement and interfacial ordering. Under comparable driving conditions, n-hexanol also exhibits higher streaming velocities than several simple hydrocarbons reported for calcite nanopores, despite the reduction in effective pore aperture caused by SAM formation. These results demonstrate that interfacial amphiphilic organization can provide a molecularly tunable boundary condition for confined transport and establish a mechanistic framework for shear-responsive lubrication in mineral nanopores.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"23 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368291","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

Influence of process-relevant impurities on the thermodynamic equilibrium of lithium hydroxide monohydrate during antisolvent crystallization with 2-propanol 2-丙醇反溶剂结晶过程中工艺相关杂质对一水氢氧化锂热力学平衡的影响

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-11-09 DOI: 10.1039/d6cp03656b

Lien Lemmens,Rayco Lommelen,Stijn Raiguel,Tom Van Gerven,Koen Binnemans

{"title":"Influence of process-relevant impurities on the thermodynamic equilibrium of lithium hydroxide monohydrate during antisolvent crystallization with 2-propanol","authors":"Lien Lemmens,Rayco Lommelen,Stijn Raiguel,Tom Van Gerven,Koen Binnemans","doi":"10.1039/d6cp03656b","DOIUrl":"https://doi.org/10.1039/d6cp03656b","url":null,"abstract":"Solid–liquid equilibria (SLE) relevant to the antisolvent crystallization of lithium hydroxide monohydrate (LiOH·H2O) from water–2-propanol mixtures were experimentally investigated in the presence of process-relevant hydroxide and chloride impurities (NaOH, KOH, LiCl, NaCl, and KCl) at 25 °C. Solubility measurements showed that NaOH, KOH, and LiCl reduce the solubility of LiOH through the common-ion effect while remaining relatively soluble themselves, indicating favorable conditions for selective LiOH·H2O crystallization. In contrast, NaCl and KCl exhibit limited solubility at higher 2-propanol mole fractions and therefore represent critical impurities that can co-crystallize with LiOH·H2O. The experimental equilibrium data were used to develop a thermodynamic model based on the Mixed-Solvent Electrolyte (MSE) framework of OLI Systems. The model accurately reproduces the experimentally observed solubility behavior and was validated using synthetic process solutions representative of industrial lithium hydroxide production routes. Antisolvent crystallization experiments confirmed the model predictions and demonstrated that high-purity LiOH·H2O can be produced from hydroxide- and LiCl-containing process streams, whereas systems containing NaCl and KCl are prone to co-crystallization of impurities. The developed model provides a quantitative tool for the design, optimization, and impurity management of industrial LiOH·H2O antisolvent crystallization processes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"9 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368280","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

Long C-N Quasi Banana Bond in an Organic Molecule: A Quadripartite Computational Investigation 有机分子中的长C-N准香蕉键：四部计算研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-11-09 DOI: 10.1039/d6cp03358j

Sanyasi Sitha

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All-metallic transistor with ultralow-power consumption and ultrafast switching speed constructed from the metalsemiconductor phase transition of zigzag germanene nanoribbons 利用之字形锗烯纳米带的金属半导体相变构建超低功耗、超快开关速度的全金属晶体管

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-11-09 DOI: 10.1039/d6cp03775e

Huan Xiao,Xingyi Tan,Jing Wan,Gang Xu,Qiang Li

{"title":"All-metallic transistor with ultralow-power consumption and ultrafast switching speed constructed from the metalsemiconductor phase transition of zigzag germanene nanoribbons","authors":"Huan Xiao,Xingyi Tan,Jing Wan,Gang Xu,Qiang Li","doi":"10.1039/d6cp03775e","DOIUrl":"https://doi.org/10.1039/d6cp03775e","url":null,"abstract":"All-metallic field-effect transistors (FETs) have remained a persistent focus of scientific exploration because they can be scaled down to smaller dimensions while maintaining low energy consumption and superior performance at higher operating frequencies. In this paper, we propose an innovative all-metallic FET based on the metal-semiconductor phase transition of zigzag germanene nanoribbons (ZGeNRs), enabling efficient on-off switching through controlled electric field modulation. The first-principles quantum transport simulations revealed that ZGeNRs-based FETs with gate lengths of 12, 10, 8, and 6 nm successfully fulfill the key performance requirements established by the 2013 International Technology Roadmap for Semiconductors (ITRS) for highperformance devices targeted for the 2028 technology node. Furthermore, the resulting power-delay product (PDP) and delay time (τ) values were substantially lower than those reported for nearly all existing transistor technologies. The decrease in PDP and τ stems from a higher density of states of ZGeNRs boosting carrier concentration, which allows for a lower supply voltage and consequently diminishes both metrics. ZGeNRs-based FETs have extraordinary potential for next-generation electronic technologies requiring high performance, ultra-low power consumption, and ultrafast switching, positioning them as a highly promising platform for future nanoelectronic applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"16 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368263","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

Fe–vacancy complexes in KDP: contrasting force partitioning reveals the Fe 3d–O 2p hybridization bottleneck KDP中的Fe空位配合物：对比力分配揭示了Fe 3d - o2p杂化瓶颈

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-11-09 DOI: 10.1039/d6cp03408j

Wenkang Yu,Xiaoning Guan,Weijun Wang,Yue Cheng,Chunlian Xiong,Xunzhe Zhang,Jinkang Yu,Zhengjun Wang,Jiangzhou Xie,Yaxin Xu,Amondulloi Burhonzoda,Changcheng Chen,Pengfei Lu

{"title":"Fe–vacancy complexes in KDP: contrasting force partitioning reveals the Fe 3d–O 2p hybridization bottleneck","authors":"Wenkang Yu,Xiaoning Guan,Weijun Wang,Yue Cheng,Chunlian Xiong,Xunzhe Zhang,Jinkang Yu,Zhengjun Wang,Jiangzhou Xie,Yaxin Xu,Amondulloi Burhonzoda,Changcheng Chen,Pengfei Lu","doi":"10.1039/d6cp03408j","DOIUrl":"https://doi.org/10.1039/d6cp03408j","url":null,"abstract":"A critical missing step in understanding how Fe impurities lower the laser damage threshold of potassium dihydrogen phosphate (KH2PO4, KDP) crystals is the transduction of sub-bandgap photon absorption into localized structural instability, which provides the initial structural driving force for material failure. Using first-principles constrained-occupation ΔSCF calculations, we investigate two charge-compensated FeK-vacancy complexes and find that the nature of the compensating vacancies partitions the photoexcited driving force in fundamentally distinct ways in the 64-atom supercell studied here: K-vacancy compensation disperses the force throughout the PO4 framework, whereas H-vacancy compensation concentrates it within the Fe–O coordination shell. Fluorine substitution, introduced as an extreme stress test, disrupts the Fe 3d–O 2p hybridization and collapses the defect-assisted optical absorption and photoexcited forces, regardless of the targeted oxygen site. The spatial pattern of this suppression is compensation-dependent: the framework-mediated pathway is most fragile at its PO4 nodes, while the shell-localized pathway is most fragile at its Fe–O core. These findings identify the Fe 3d–O 2p hybridization architecture, shaped by the vacancy environment, as the bottleneck that governs the coupling of optical excitation to structural forces, and point to this hybridization as a pivotal control point for mitigating photoexcited structural responses in KDP.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"19 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368285","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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Experimental and Theoretical Exploration of Photophysics and Photochemistry of meso-(phenoxymethyl)-BODIPY-Based Model Compound 介位（苯氧甲基）- bodipy模型化合物光物理和光化学的实验与理论探索

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-11-09 DOI: 10.1039/d6cp01495j

Sasipreetham Devarakonda,Atanu Bhattacharya,Gowri Sankar Reddipalli,Balakrishna Kolli,Qazi Saifullah,Partha Roy,Suman Das,Manoj P. Rayaroth

{"title":"Experimental and Theoretical Exploration of Photophysics and Photochemistry of meso-(phenoxymethyl)-BODIPY-Based Model Compound","authors":"Sasipreetham Devarakonda,Atanu Bhattacharya,Gowri Sankar Reddipalli,Balakrishna Kolli,Qazi Saifullah,Partha Roy,Suman Das,Manoj P. Rayaroth","doi":"10.1039/d6cp01495j","DOIUrl":"https://doi.org/10.1039/d6cp01495j","url":null,"abstract":"Photoactivated chemotherapy (PACT) enables controlled drug release independent of oxygen, offering advantages over photodynamic therapy. Here, we study a meso-(phenoxymethyl)-substituted BODIPY (m-BODIPY-OPh) as a model photocage. Spectroscopic characterization shows strong visible absorption (~516 nm) and high fluorescence. Photolysis experiments reveal multiple pathways, including desired -OPh release alongside competing -CH₃ and -F elimination. Quantum chemical calculations (TDDFT, CASSCF, CASPT2) and nonadiabatic dynamics simulations show that C-O bond cleavage is not directly accessible from the S₁ state due to a significant energy barrier and absence of a barrierless pathway or conical intersection. Instead, excitation leads primarily to structural relaxation and long-lived fluorescence. These results demonstrate that spectral tuning alone is insufficient for effective PACT. Efficient, bond-selective drug release requires precise control of excited-state reaction pathways, providing key design insights for next-generation BODIPY-based photocages..","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368282","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 Multifunctionality of CdBiS2Cl monolayer: Insights into Negative Poisson’s Ratio and Piezo-photocatalysis 揭示CdBiS2Cl单层的多功能性：对负泊松比和压电光催化的见解

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-11-09 DOI: 10.1039/d6cp02452a

Nilakantha Tripathy,Fathima IS,Harshita Seksaria,Abir De Sarkar

{"title":"Unveiling the Multifunctionality of CdBiS2Cl monolayer: Insights into Negative Poisson’s Ratio and Piezo-photocatalysis","authors":"Nilakantha Tripathy,Fathima IS,Harshita Seksaria,Abir De Sarkar","doi":"10.1039/d6cp02452a","DOIUrl":"https://doi.org/10.1039/d6cp02452a","url":null,"abstract":"The integration of multifunctionality has emerged as a key strategy in advancing modern technologies, especially within the realm of two-dimensional (2D) materials. Using first-principles calculations, the negative Poisson’s ratio (NPR) in the in-plane and out-of-plane direction and piezo-photocatalysis in CdBiS2Cl monolayer (ML) have been demonstrated. An IP NPR of -0.056 is identified at θ = 42.5° close to the diagonal axis of the ML, signifying auxetic behaviour. This auxetic behaviour stems from the ML’s puckered structural motif and unique deformation mechanism, contributing to its low elastic constants and strong elastic anisotropy. The polarity of the out-of-plane (Poisson’s ratio) PRs (v_zx and v_zy) is dictated by the atomic composition of the outermost layer, whether it is Bi or Cl. The ML also exhibits favourable band alignments for redox reactions associated with water splitting, achieving 11.33% solar-to-hydrogen efficiency, exceeding that of many conventional photocatalysts. Its intrinsic piezoelectricity (d_21= -4.28 pm/V and d_22= 29.68 pm/V) generate a substantial piezopotential of 62.03 V, promoting efficient charge separation and enabling piezocatalytic activity even in dark conditions. The synergistic combination of piezoelectricity with photocatalysis, termed as piezo-photocatalysis further elevates catalytic efficiency and broadens the active pH range for hydrogen and oxygen evolution reactions. These physical insights highlight CdBiS2Cl ML as a promising multifunctional material for next-generation flexible electronics, impact-resistant device applications, energy conversion technologies, and eco-friendly catalytic applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149368283","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

Modeling the Interfacial Curvature Effect of Electrode Roughness in Ionic Capacitive Pressure Sensing under Intimate Contact 密切接触下离子电容压力传感中电极粗糙度的界面曲率效应建模

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-11-07 DOI: 10.1039/d6cp03748h

Wei Zeng,Ruohong Yin,Qinji He,Aoxiang Liang,Bo Li,Yi Xiong,Sakil Mahmud

{"title":"Modeling the Interfacial Curvature Effect of Electrode Roughness in Ionic Capacitive Pressure Sensing under Intimate Contact","authors":"Wei Zeng,Ruohong Yin,Qinji He,Aoxiang Liang,Bo Li,Yi Xiong,Sakil Mahmud","doi":"10.1039/d6cp03748h","DOIUrl":"https://doi.org/10.1039/d6cp03748h","url":null,"abstract":"Capacitive pressure sensors commonly exploit surface roughness to increase contact area and enhance sensitivity; however, the role of electrode roughness after intimate electrode–dielectric contact is established remains poorly understood. Here, a two-dimensional multiphysics finite-element framework has been developed integrating solid mechanics, electrostatics, and ionic transport to elucidate the influence of electrode surface morphology in an interdigital ionic capacitive pressure sensor under intimate contact. The simulations reveal a two-stage mechanical response with a transition near 30 kPa, corresponding to the ionic hydrogel dielectric reaching the electrode-top plane, and show that macroscopic deformation is largely insensitive to electrode roughness. Additional mechanical sweeps refine the reference transition to 28 kPa and show its dependence on electrode thickness, hydrogel modulus, and substrate support. In contrast, roughness strongly modulates the interfacial electric field and ion redistribution. Increasing roughness intensifies the absolute local electric field but suppresses its pressure-induced variation through a curvature effect, thereby reducing the electrochemical driving force for ion redistribution. Mean-field and local curvature analyses support this interpretation. A near-smooth interface (A = 0.01W) achieves the highest predicted sensitivity of 10.832 MPa−1 at 0–30 kPa, whereas a smooth interface (A = 0W) provides the highest predicted sensitivity of 2.820 MPa−1 at 30–170 kPa. These findings suggest interfacial field modulation, rather than contact-area expansion, as a critical design parameter for ionic capacitive sensors operating under the modeled intimate contact conditions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"21 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360230","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

Correlating the distribution of site energies, activation energies and saddle point energies in the energy landscape of a lithium borate glass. 硼酸锂玻璃能量格局中位能、活化能和鞍点能的分布关系。

IF 3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-11-06 DOI: 10.1039/d6cp02822e

Mohammad Ali Badragheh, Michael Vogel, Martin Schäfer, Karl-Michael Weitzel

引用次数: 0

The SHEF1552 dataset: Fundamental trends and physical insights into halogen, chalcogen, pnictogen and tetrel bonds SHEF1552数据集：卤素，硫，烟原和四元键的基本趋势和物理见解

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2026-11-06 DOI: 10.1039/d6cp04299f

Harry Nash,Lee Brammer,Grant Hill

{"title":"The SHEF1552 dataset: Fundamental trends and physical insights into halogen, chalcogen, pnictogen and tetrel bonds","authors":"Harry Nash,Lee Brammer,Grant Hill","doi":"10.1039/d6cp04299f","DOIUrl":"https://doi.org/10.1039/d6cp04299f","url":null,"abstract":"The Sigma-Hole Energies and additional Factors (SHEF1552) dataset, a comprehensive collection of 1,552 σ -hole interactions (halogen, chalcogen, pnictogen, and tetrel bonds) is introduced. Each complex, formed by pairing 82 σ -hole donors with 19 Lewis bases, was analysed using explicitly correlated coupled-cluster interaction energies and symmetry-adapted perturbation theory (SAPT). Analysis of this dataset identifies key geometric and energetic trends. Pnictogen bonds are, on average, the strongest interactions, followed by tetrel, chalcogen, and halogen bonds. The interaction energy-distance relationship exhibits a distinct boomerang-like distribution, defining two regimes of contact strength. Geometrically, while halogen, chalcogen, and tetrel bonds require σ -hole angles approaching 180° for short contacts, pnictogen bonds are unique, displaying no requirement for linearity at short distances. Additionally, roughly 5% of the complexes exhibit appreciable interaction energies despite intermolecular distances exceeding the sum of their van der Waals radii, confirming that strict distance cut-offs are overly restrictive. Finally, SAPT analysis shows the strongest σ -hole interactions are electrostatically dominated, whereas the weakest are primarily dispersion-driven. Beyond these physical insights, the SHEF1552 dataset can serve as a wide-ranging computational benchmark for geometries and energies of σ -hole interactions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"28 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149360403","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