Physical Chemistry Chemical Physics最新文献

{"title":"Pure spin currents induced by asymmetric H-passivation in B3C2P3 nanoribbons†","authors":"Jing-Jing He, Jia-Bei Dong, Ling-Xiao Liu, Qin-Yue Cao, Jun-Yi Gu, Ying Zhang, Min Hua, Jia-Ren Yuan and Xiao-Hong Yan","doi":"10.1039/D4CP03033H","DOIUrl":"10.1039/D4CP03033H","url":null,"abstract":"<p >Inspired by the recently reported novel two-dimensional material B<small>₃</small>C<small>₂</small>P<small>₃</small>, we performed one-dimensional shearing along the zigzag direction to obtain four B<small>₃</small>C<small>₂</small>P<small>₃</small> nanoribbons with various edge atom combinations. An asymmetric hydrogen passivation scheme was employed to modulate the electronic properties and successfully open the band gap, especially the 2H-1H passivation with dihydrogenation and monohydrogenation at the top and bottom edges, respectively, achieving bipolar magnetic semiconductors with edge P-atoms contributing to the main magnetism. Furthermore, three crucial spin-polarized transmission spectra yielded a significant spin-dependent Seebeck effect (SDSE), displaying superior thermoelectric conversion capabilities by generating pure spin currents. Our work shows that this asymmetric H-passivation effectively enables the enhancement of the spin caloritronic transport properties of the B<small>₃</small>C<small>₂</small>P<small>₃</small>, which is of great significance for the exploitation of novel materials and their applications in spintronics.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 1","pages":" 589-595"},"PeriodicalIF":2.9,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797689","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}

{"title":"Potential thermoelectric material Tl3XS4 (X = V, Nb, Ta) with ultralow lattice thermal conductivity†","authors":"Xiefei Song, Guangzhao Wang, Wenzhong Li, Siyu Gan, Yan Cai, Dianxu Ma, Yuhui Luo, Yao He and Ning Wang","doi":"10.1039/D4CP04000G","DOIUrl":"10.1039/D4CP04000G","url":null,"abstract":"<p >The demand for sustainable energy solutions has driven intensive research into advanced thermoelectric (TE) materials, to harness waste heat for efficient power generation. Recently, several studies have revealed that Tl<small>₃</small>VS<small>₄</small> possesses an ultralow lattice thermal conductivity, despite its simple body-centered cubic lattice structure. This paper focuses on the TE properties of Tl<small>₃</small>XS<small>₄</small> (X = V, Nb, Ta) compounds through a systematic exploration utilizing first-principles calculations and semiclassical Boltzmann transport theory. The results of the AIMD simulation and phonon calculation reveal the excellent dynamic stability and thermal stability of Tl<small>₃</small>XS<small>₄</small> at 300, 500, and 700 K. Moreover, we find that the Tl<small>₃</small>XS<small>₄</small> compounds present ultralow lattice thermal conductivity (&lt;0.5 W m<small>⁻¹</small> K<small>⁻¹</small> at 300 K), and the nanostructure strategy is effective. Based on the outstanding Seebeck coefficient and ultralow lattice thermal conductivity, the optimal <em>ZT</em> values of Tl<small>₃</small>VS<small>₄</small>, Tl<small>₃</small>NbS<small>₄</small>, and Tl<small>₃</small>TaS<small>₄</small> at 300 K are determined to be 1.17 (p-type), 0.84 (n-type), and 0.65 (p-type), respectively. Additionally, at each considered temperature, the maximum <em>ZT</em> values of p-type (n-type) Tl<small>₃</small>XS<small>₄</small> follow the order: Tl<small>₃</small>VS<small>₄</small> &gt; Tl<small>₃</small>NbS<small>₄</small> &gt; Tl<small>₃</small>TaS<small>₄</small> (Tl<small>₃</small>NbS<small>₄</small> &gt; Tl<small>₃</small>VS<small>₄</small> &gt; Tl<small>₃</small>TaS<small>₄</small>). Our results demonstrate that Tl<small>₃</small>XS<small>₄</small> (X = V, Nb, Ta) compounds are promising thermoelectric materials. This exhaustive research enhanced our nuanced comprehension of the electronic, dynamic, and thermoelectric attributes of Tl<small>₃</small>XS<small>₄</small> (X = V, Nb, Ta), thereby offering valuable insights into the TE field.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 1","pages":" 539-549"},"PeriodicalIF":2.9,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797698","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}

{"title":"Exploring buoyancy-driven effects in chemo-hydrodynamic oscillations sustained by bimolecular reactions","authors":"Adam Bigaj, Marcello Budroni, Laurence Rongy","doi":"10.1039/d4cp03617d","DOIUrl":"https://doi.org/10.1039/d4cp03617d","url":null,"abstract":"Exotic dynamics, previously associated only with reactions involving complex kinetics, have been observed even with simple bimolecular reactions A + B → C, when coupled with hydrodynamical flows. Numerical studies in two-dimensional reactors have shown that oscillatory dynamics can emerge from an antagonistic coupling between chemically-driven buoyancy and Marangoni convective flows, induced by changes in density and surface tension, respectively, as the reaction occurs. Here, we investigate reactions increasing both surface tension and density, leading to a cooperative coupling between the flows and show how, in this configuration, buoyancy-driven contribution dampens spatio-temporal oscillations of concentration. We finally identify the key parameters controlling the onset and persistence of the oscillatory instability, namely the density and surface tension gradients, and the system’s height.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"14 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797697","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}

{"title":"Insights into the structural complexity and local disorder of crystalline AsTe3 from Semi-Automated First-Principles Modelling","authors":"Sylvian Cadars, Olivier Masson, jean-paul laval, Firas Elkheir Shuaib, Gaelle Delaizir, Assil Bouzid, Andrea Piarristeguy","doi":"10.1039/d4cp02941k","DOIUrl":"https://doi.org/10.1039/d4cp02941k","url":null,"abstract":"A semi-automated workflow relying on atomic-scale modelling is introduced to explore and understand the yet-unsolved structure of the crystalline AsTe<small>₃</small> material, recently obtained from crystallization of the parent AsTe<small>₃</small> glass, which shows promising properties for thermoelectric applications. The seemingly complex crystal structure of AsTe<small>₃</small> is approached with density functional theory, from the stand point of As/Te disorder, in a structural template derived from elemental-Te (Te<small>_el</small>), following experimental findings from combined X-ray total scattering and diffraction. Our workflow includes a combinatorial structure generation step followed by successive structure selection and relaxation steps with progressively-increasing accuracy levels and a muti-criteria evaluation procedure. A small set of high quality models with common structural features emerge, all consisting of intergrowth domains typically below 1 nm in thickness and with the local compositions and structures of Te<small>_el</small> and α-As<small>₂</small>Te<small>₃</small>, but with different thicknesses and relative arrangements, which points to the presence of such defects in crystalline AsTe<small>₃</small>. While predictions of the electronic bandgaps are in excellent agreement with the experimental value for our best models, we find that some of these defects may be associated with locally-increased density of states around the Fermi level, potentially contributing to the overall electronic conductivity, which, along with intrinsic structural complexity, is among the key features of the reported outstanding thermoelectric properties of this compound.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797692","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}

{"title":"A Water-Responsive Calix[4]Resorcinarene System: Self-Assembly and Fluorescence Modulation","authors":"María Virginia Virginia Sosa, Kashif Hussain, Eduardo D Prieto, Tatiana Da Ros, Muhammad Raza Shah, Fernando Sebastian Garcia Einschlag, Ezequiel Wolcan","doi":"10.1039/d4cp04011b","DOIUrl":"https://doi.org/10.1039/d4cp04011b","url":null,"abstract":"This study explores how water content modulates the self-assembly and fluorescence behavior of two novel calix[4]resorcinarene macrocycles. These macrocycles transition from large, flattened structures in pure THF to large giant vesicles (500-5000 nm) coexisting with small micelles (3.4-3.5 nm) as the water percentage in THF/water mixtures increases up to 53%. At higher water percentages, the assemblies become smaller, forming unimodal micelles with diameters of approximately 140-160 nm. Fluorescence quenching is observed upon water addition, attributed to nonradiative deactivation. These findings highlight water as a key regulator of the assembly and fluorescence of these calix[4]resorcinarene macrocycles, paving the way for further development of water-responsive calixarene systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"21 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797695","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}

{"title":"Elucidation of the Co4+ State with Strong Charge-Transfer Effects in Charged LiCoO2 by Resonant Soft X-ray Emission Spectroscopy at the Co L3 edge","authors":"Daisuke Asakura, Takaaki Sudayama, Yusuke Nanba, Eiji Hosono, Hisao Kiuchi, Kosuke Yamazoe, Jun Miyawaki, Yoshihisa Harada, Atsuo Yamada, Ru-Pan Wang, Frank M F de Groot","doi":"10.1039/d4cp03759f","DOIUrl":"https://doi.org/10.1039/d4cp03759f","url":null,"abstract":"To understand the electronic-structure change of LiCoO<small>₂</small>, a widely used cathode material in Li-ion batteries, during charge–discharge, we performed ex situ soft X-ray absorption spectroscopy (XAS) and resonant soft X-ray emission spectroscopy (RXES) of the Co L<small>₃</small> edge in combination with charge-transfer multiplet calculations. The RXES profile significantly changed for the charged state at 4.2 V vs. Li/Li<small>⁺</small>, corresponding to the oxidation reaction from a Co<small>³⁺</small> low-spin state for the initial state, while the XAS profile exhibited small changes. For the 4.2-V charged state, we confirmed that approximately half of the initial Co<small>³⁺</small> ions were oxidized to Co<small>⁴⁺</small> ions. The multiplet calculation of the RXES results revealed that the Co<small>⁴⁺</small> state has a negative charge-transfer energy and the d<small>⁶</small><span><style>text-decoration:underline\"</style>L</span> state (<span><style>text-decoration:underline\"</style>L</span> is a ligand hole) is the most stable. Therefore, the O 2p hole created by the strong charge-transfer effect plays a major role in the redox reaction of LiCoO<small>₂</small>.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"98 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805142","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}

{"title":"Assignment of IR spectra of ethanol at Brønsted sites of H-ZSM-5 to monomer adsorption using a Fermi resonance model†","authors":"Dipanshu Kumar, Joachim Sauer, Alessia Airi, Silvia Bordiga and Daria Ruth Galimberti","doi":"10.1039/D4CP03861D","DOIUrl":"10.1039/D4CP03861D","url":null,"abstract":"<p >Understanding how alcohol molecules interact with the Brønsted acid sites (BAS) of zeolites is a prerequisite to the design of zeolite catalysts and catalytic processes. Here, we report IR spectra for the adsorption of ethanol on a highly crystalline sample of H-ZSM-5 zeolites exposed to ethanol gas at increasing pressure. We use density functional theory in combination with a FERMI resonance model to assign the measured spectra to a single adsorbed ethanol molecule per BAS. Specifically, we assign the bands at 2450 cm<small>⁻¹</small> and 1670 cm<small>⁻¹</small> to a FERMI resonance between the fundamental (Z)O–H stretching band of a single-ethanol-loaded BAS and the first overtone of the (Z)O–H out-of-plane bending. We conclude that adsorbed dimers do not contribute in a noticeable way up to a concentration of almost one ethanol molecule per BAS site. We further show that hybrid functionals (B3LYP) are required to get a close match between the predicted and experimental spectra, whereas commonly used generalized gradient type functionals such as PBE incorrectly describe the potential energy surface. They overestimate the redshift of the OH stretching band on hydrogen bond formation which results in an erroneous assignment of the IR bands.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 1","pages":" 550-563"},"PeriodicalIF":2.9,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cp/d4cp03861d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797314","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"2D Co-Anti MXenes (CoB/CoP) as Promising Anode Materials for Magnesium-Ion Batteries in Diglyme and Triglyme Electrolytes: A First-Principles Study","authors":"Nandhini Panjulingam, Senthilkumar Lakshmipathi","doi":"10.1039/d4cp03358b","DOIUrl":"https://doi.org/10.1039/d4cp03358b","url":null,"abstract":"Magnesium-ion batteries have the probability of the future replacement of commercially available Li-ion batteries due to their lower cost and sustainability. On the other hand, magnesium ions are dendrite-free and offer greater energy density and volumetric capacity due to their divalent nature. Conventional electrode materials face challenges in capturing magnesium ions. We assessed the feasibility of Co-Anti MXenes (CoB/CoP) monolayers as electrode materials for Mg-ion batteries using density functional theory. The adsorption energy of CoB for Mg atoms is -2.84 eV at vacuum (-4.58 and -4.65 eV for diglyme and triglyme effect calculated using the Vaspsol method), respectively. The Ab initio molecular dynamics (AIMD) simulation of Mg8Co18B18 was performed at 300 K, signifying their high stability in the magnesium process at ambient temperature. Diffusion coefficient 3.57 x 10-7 cm2/s was determined at ambient temperature 300 K. The electrical conductivity per relaxation time (Mg8Co18B18) at 300 K is found to be 1.64×1019(Ω m s) with corresponding chemical potential -6.94 eV respectively. The Co-Anti MXenes have the potential to be used as an anode material in Mg-ion batteries.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"69 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793515","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}

{"title":"Twin hydrogen bonds with phosphine oxides: anticooperativity effects caused by competing proton donors","authors":"Mikhail A. Kostin, Omar Alkhuder, Ruslan Asfin, Peter Tolstoy","doi":"10.1039/d4cp04041d","DOIUrl":"https://doi.org/10.1039/d4cp04041d","url":null,"abstract":"In this computational work we study complexes with two equivalent intermolecular hydrogen bonds formed between Me<small>₃</small>PO and two identical proton donors (“twin” hydrogen bonds) for the set of 70 proton donor molecules. The changes of phosphorus chemical shift and vibrational frequency of P=O group upon complexation correlate quite good with the total strength of two hydrogen bonds. The set of explicit numerical dependences is proposed for assessing interatomic distances and hydrogen bond strengths from spectral data. Comparison with the results obtained for analogous previously studied 1:1 complexes allowed us to analyze in detail anticooperativity effects on the geometry, energy and spectral parameters. Two hydrogen bonds compete for PO acceptor group and their mutual weakening increases nonlinearly with strengthening of the complex, reaching approximately 25% in energy (which corresponds to 0.1 Å lengthening for short strong H-bonds), which is clearly seen in NMR and IR spectra and correlates well with the changes of the spectral parameters.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"82 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793520","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}

{"title":"Design of bisamide inhibitors of the TASK-1 potassium channel in silico†","authors":"Lu Liu, Jixiang Liu, Liang Chen, Risong Na, Lianjuan Yang, Xiaoping Liu and Xi Zhao","doi":"10.1039/D4CP03521F","DOIUrl":"10.1039/D4CP03521F","url":null,"abstract":"<p >TWIK-related acid-sensitive potassium channel 1 (TASK-1) is expressed ubiquitously across various tissues and plays a significant role in neural activity and anesthetic modulation, making it a crucial target for pharmaceutical research. The high conservation of binding site residues within the TASK family, particularly between TASK-1 and TASK-3, necessitates the development of selective inhibitors for TASK-1. In this study, we utilized a combination of structure-based drug design (SBDD) and ligand-based drug design (LBDD) approaches. Initially, several bisamide-centered molecules were designed using the program MolAICal, which is recognized for its ability to generate selective inhibitors containing bisamide segments, and conducted preliminary screening <em>via</em> molecular docking. Subsequently, 3D-QSAR models were developed for 56 bisamide derivatives targeting TASK-1 and TASK-3, with the models exhibiting robust predictive capabilities (TASK-1: <em>Q</em><small>²</small> = 0.61, <em>R</em><small>²</small><small>_pred</small> = 0.84; TASK-3: <em>Q</em><small>²</small> = 0.60, <em>R</em><small>²</small><small>_pred</small> = 0.71). Using these models, the candidate molecules were subjected to activity prediction and subsequent filtering. Ultimately, molecular dynamics simulations, coupled with free energy calculations, pinpointed two bisamide-core molecules with favorable ADMET properties as potential selective inhibitors for TASK-1. Furthermore, molecular dynamics simulations revealed the critical role of the key residue Leu122 in conferring selectivity to bisamide compounds for TASK-1 channel proteins.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 1","pages":" 451-462"},"PeriodicalIF":2.9,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793658","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}