Physical Chemistry Chemical Physics最新文献_第9页

Structure effect of the bipyrazol derivatives on corrosion inhibition of mild steel in 1M HCl: Weight loss, electrochemical measurements, XPS/SEM surface analysis, DFT and MC simulation

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-10 DOI: 10.1039/d4cp02946a

N. Setti, A. Barrahi, M. Maatallah, Y. Kaddouri, R. Touzani, Abdelkader Zarrouk, A. Dafali, Burak Dikici, Khalid Karrouchi, Hatem A. Abuelizz

{"title":"Structure effect of the bipyrazol derivatives on corrosion inhibition of mild steel in 1M HCl: Weight loss, electrochemical measurements, XPS/SEM surface analysis, DFT and MC simulation","authors":"N. Setti, A. Barrahi, M. Maatallah, Y. Kaddouri, R. Touzani, Abdelkader Zarrouk, A. Dafali, Burak Dikici, Khalid Karrouchi, Hatem A. Abuelizz","doi":"10.1039/d4cp02946a","DOIUrl":"https://doi.org/10.1039/d4cp02946a","url":null,"abstract":"The inhibitory study of 4-(bis((1H-pyrazol-1-yl) methyl) amino) phenol (2PzH) and 4-(bis(3,5-dimethyl-1H-pyrazol-3-ylmethyl)amino] phenol (2PzMe) on mild steel (M-S) corrosion in 1M HClaggressive medium was conducted via, electrochemical techniques, thermodynamic parameters, XPS and SEM analysis. In fact, dissolution thermodynamic parameters and adsorption processes were worked out using the temperature change in gravimetric measurements. Obviously, the inhibition efficacy rises with the rise in 2PzH concentration to get to 95.7% and 2PzMe to get to 95.9% at 10-3M. The polarization measurement (PDP) also argued that these compounds are the mixed inhibitors. EIS measurements have divulged that the charge transfer resistance increased with the increase in inhibitor concentration. The bipyrazolic compounds were adsorbed on the steel surface as stated by the Langmuir adsorption model which was presented by chemisorption. These results were further strengthened by elemental characterization of the metal/solution contact employing XPS, for the two molecules tested. SEM technique disclosed the passive film forming on the metallic surface. The computational approach was computed utilizing the DFT method and Monte Carlo/Molecular dynamic (MC/MD) analysis to treat both the structure of 2PzH and 2PzMe in order to link the electron properties to the both compounds’ adsorption and inhibitory actions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375237","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

Aromatic Trails. Persistence and Interplay Between Linked Spherical Aromatic Dicarboranes in Dimer to Hexamer Linear Arrays

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-10 DOI: 10.1039/d4cp03930k

Alvaro Muñoz-Castro

{"title":"Aromatic Trails. Persistence and Interplay Between Linked Spherical Aromatic Dicarboranes in Dimer to Hexamer Linear Arrays","authors":"Alvaro Muñoz-Castro","doi":"10.1039/d4cp03930k","DOIUrl":"https://doi.org/10.1039/d4cp03930k","url":null,"abstract":"The consecutive crack-link between well-defined building blocks is a plausible strategy in developing molecularly conceived materials. Here, we evaluate the resulting behavior of dimer to hexamer linear arrays based on linking spherical aromatic para-[C2B10H10] clusters (1) as relevant motifs toward understanding the characteristics of extended linear materials. Our results exhibit the persistence of spherical aromatic properties from the parent building block as isolated spherical aromatic states within the overall structure. Under different orientations of the applied field, the multiple enabled shielding cones at each linked cluster can evolve from a perfectly parallel disposition to an enhanced overlap under rotation. In addition, large values of NICS isosurfaces serve to locate the independent spherical aromatic states, whereas the use of anisotropy (NICSaniso) recovers the resulting isotropic regions at such states within the overall linear structure. Such behavior is expected to be envisaged in extended linear arrays and non-covalently interacting scenarios, such as self-assembled monolayers. Our results encourage further quests for understanding the interplay between different linked aromatic states, envisaging and unraveling the overall behavior of extended architectures designed by connecting aromatic building units.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"32 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375309","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

In2F2 monolayer: a new class of two-dimensional materials with negative Poisson's ratio and topological phase†

IF 2.9 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-10 DOI: 10.1039/D4CP04871G

Shahram Yalameha, Javad Zahmatkesh, Fatemeh Zamanian and Zahra Nourbakhsh

{"title":"In2F2 monolayer: a new class of two-dimensional materials with negative Poisson's ratio and topological phase†","authors":"Shahram Yalameha, Javad Zahmatkesh, Fatemeh Zamanian and Zahra Nourbakhsh","doi":"10.1039/D4CP04871G","DOIUrl":"10.1039/D4CP04871G","url":null,"abstract":"Two-dimensional (2D) materials have garnered significant attention for their exceptional potential in electronic, optical, and flexible nanodevices. In this study, we introduce a novel 2D In2F2 monolayer, revealed through first-principles calculations, and demonstrate its thermal, dynamic, and mechanical stability. Our findings show that the In2F2 monolayer exhibits notable anisotropic mechanical behavior, including auxetic properties characterized by a negative Poisson's ratio. Electronic band structure calculations, using both PBE–GGA and HSE06 functionals, indicate that this monolayer is a semiconductor with a small, nontrivial topological bandgap of approximately 1.58 meV. The observed s–p band inversion and calculated <img> invariant, confirm the presence of a nontrivial topological phase in this material. Furthermore, the optical absorption spectrum reveals strong anisotropy, with significant absorption in the visible to near-infrared range along the y-axis, suggesting potential applications in polarized photodetectors and anisotropic optoelectronic devices. The relatively low work function (3.86 eV) further increases its suitability for electron-emission applications, such as thermionic devices. These mechanical, electronic, and optical properties position the In2F2 monolayer as a promising candidate for next-generation electronics, flexible electronics, and anisotropic optoelectronics.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 8","pages":" 4407-4418"},"PeriodicalIF":2.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375181","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

Puppeteering the Reactivity of Frustrated Lewis Pairs toward CO2 via Coordination Dichotomy in Bridging Units

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-10 DOI: 10.1039/d5cp00020c

Mohmmad Faizan, Ravinder Pawar

引用次数: 0

Temperature and concentration dependence of the ionic charge transfer between solid and liquid Li+-electrolytes -- The systems LLZO:Ta/LiPF6-EC-DMC, LATP/LiPF6-EC-DMC and LLZO:Ta/LiBOB-DME-THF

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-10 DOI: 10.1039/d4cp04738a

Tobias Wekking, Martin Finsterbusch, C. Korte

{"title":"Temperature and concentration dependence of the ionic charge transfer between solid and liquid Li+-electrolytes -- The systems LLZO:Ta/LiPF6-EC-DMC, LATP/LiPF6-EC-DMC and LLZO:Ta/LiBOB-DME-THF","authors":"Tobias Wekking, Martin Finsterbusch, C. Korte","doi":"10.1039/d4cp04738a","DOIUrl":"https://doi.org/10.1039/d4cp04738a","url":null,"abstract":"The kinetics of the electrochemically driven lithium ion (Li+) transfer from a liquid Li+ electrolyte to a solid (ceramic) Li+ electrolyte is investigated. A DC polarisation is applied to measure the current density ivs. the drop of the electrochemical potential Δμ~Li+ of Li+ ions at the interface. LLZO:Ta and LATP were chosen in this study as the two most promising oxide-ceramic electrolytes and combined with LiPF6 in EC/DMC (1:1) and LiBOB in THF/DME (1:1) as most relevant liquid electrolytes. To determine the rate limiting step of the Li+ transfer across the interface, the results were modelled using a combination of a constant ohmic resistance and a current dependent, thermally activated ion Butler-Volmer like transfer process. At low Li+ concentration in the liquid electrolyte the Butler-Volmer like transfer process is rate limiting, while at high Li+ concentration the low conducting surface layer on the solid electrolyte. The areal resistance of the low conducting surface layer is in the order of 600 Ω cm2 (25 °C) for LLZO:Ta, and thus about three times higher compared to LATP. The activation energy of the ionic transport in the low conducting surface layer is about twice compared to the solid electrolytes LLZO:Ta and LATP. The exchange current density the Butler-Volmer like transfer process is in the order of 100−300 μA cm-2 (25 °C, 1 mol l-1 Li+. There is a symmetric transition state (α ≈ 1/2).","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"9 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375183","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

Evidence for Near-Superionic Conductivity in the Li3BS3 Electrolyte and Insights on the Lithium Orthothioborate Transport Mechanisms

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-10 DOI: 10.1039/d4cp03771e

Aarya Riasati, Tridip Das, William A. Goddard III

引用次数: 0

Energy Decomposition Analysis for excited states: An Extension based on TDDFT

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-10 DOI: 10.1039/d4cp04207g

Florian Kreuter, Ralf Tonner-Zech

{"title":"Energy Decomposition Analysis for excited states: An Extension based on TDDFT","authors":"Florian Kreuter, Ralf Tonner-Zech","doi":"10.1039/d4cp04207g","DOIUrl":"https://doi.org/10.1039/d4cp04207g","url":null,"abstract":"To enhance the understanding of photochemical reactivity and its mechanisms, it is essential to analyze bonding interactions in excited-state reactions. Such insights can aid in optimizing these reactions. This paper presents an energy decomposition analysis method for excited states (exc-EDA), integrating the ground state EDA approach by Morokuma, Ziegler and Rauk with time-dependent density functional theory (TDDFT). The methodology focuses on calculating excitation energies, particularly for the intermediate states of the EDA. We introduce two variants: the first uses non-relaxed excitation coefficients (exc-u-EDA), where the excitation coefficients of the excited fragment are used directly; the second optimizes these coefficients for the intermediate states (exc-r-EDA). Exc-EDA can be applied with various density functionals, but the accuracy depends on the functional’s ability to describe the excited state properly. Smaller basis sets result in lower energy values due to fewer virtual orbitals, while larger basis sets produce consistent relative results but may involve different excited states in intermediate steps leading to artificial increase of energy terms in the EDA. The method’s convergence behavior resembles that of TDDFT, with a computational cost approximately three times that of the underlying TDDFT calculation. Application of exc-EDA to singlet fission in pentacene clusters demonstrates its practical value, offering quantitative insights into excited-state bonding and revealing clear, intuitive trends.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375236","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

The effect of Electron doping in non magnetic YH3 Leading to Room Temperature Ferromagnetism and Flat Band: Insights from Density functional theory

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-10 DOI: 10.1039/d4cp03859b

Pratap Mane, Ravi Kumar Trivedi, Parthasarathy Velusamy, Brahmananda Chakraborty

{"title":"The effect of Electron doping in non magnetic YH3 Leading to Room Temperature Ferromagnetism and Flat Band: Insights from Density functional theory","authors":"Pratap Mane, Ravi Kumar Trivedi, Parthasarathy Velusamy, Brahmananda Chakraborty","doi":"10.1039/d4cp03859b","DOIUrl":"https://doi.org/10.1039/d4cp03859b","url":null,"abstract":"Here, we present the induced room temperature d0ferromagnetism for YH3 doped with B (2 µB per defect magnetic moment) with the aid of Density Functional Theory (DFT) simulations. The prediction of d0 ferromagnetism in non-magnetic YH3 by Generalized Gradient Approximationfunctional has been further confirmed with the help of hybrid HSE06 functional. Interestingly, B doping in the system lead to appearance of flat band which may be attributed due to electron doping in the system. The presence of flat band on the Fermi level may lead to stable ferromagnetism in the system. We found that with a single B atom having impurity concentration of 1.04 at%, YH3 attains 2.0 µB magnetic moment per defect. The partial density of states along with spin-density plot implies that the induced magnetic moment is the result of interaction between the localized 2p, and 4d orbitals of the impurity B and host Y atoms with doped system satisfying the Stoner criteria for induced ferromagnetism. The presence of ferromagnetism in the system at room temperature has been estimated by calculating the Curie temperature, which is around Tc = 510 K by using mean field approximation. The thermodynamic and dynamic stability of the system at 25GPa has been confirmed with the Ab-initio MD and phonon dispersion. All these outcomes indicate the experimental feasibility of the system as a spintronic device and we also propose that electron doping may be a possible route to design material interesting properties.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"43 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375235","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

Using an aromatic linker to optimize charge-resonance states, photodimerization and reversibility in covalent anthracene dimers

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-10 DOI: 10.1039/d4cp04022h

Kevin Lam, Robert J. Dillon, Abel Carreras, Tomohiko Nishiuchi, Takashi Kubo, Rabih O Al-Kaysi, David Casanova, Christopher J. Bardeen

{"title":"Using an aromatic linker to optimize charge-resonance states, photodimerization and reversibility in covalent anthracene dimers","authors":"Kevin Lam, Robert J. Dillon, Abel Carreras, Tomohiko Nishiuchi, Takashi Kubo, Rabih O Al-Kaysi, David Casanova, Christopher J. Bardeen","doi":"10.1039/d4cp04022h","DOIUrl":"https://doi.org/10.1039/d4cp04022h","url":null,"abstract":"The intramolecular [4+4] photodimerization of anthracene chromophores in covalent assemblies can be harnessed to create negative photochromic systems. This paper reports the characterization of the photophysical and photochemical properties of a new class of asymmetric phenyl-linked bis(anthracene) photochromes and compares their behavior with that of a previously studied symmetric ethylene-linked analog. Steady-state and femtosecond time-resolved spectroscopic experiments show that both types of bis(anthracenes) support a neutral bright state along with a lower-energy charge resonance state. After photoexcitation, both states relax on sub-10 ps timescales, but with significantly different photodimerization quantum yields: 0.83 using 532 nm excitation of the charge-resonance state versus 0.46 for 400 nm excitation of the neutral bright state. The phenyl-linked bis(anthracene) derivatives exhibit superior thermal stability and reversibility due to a lower activation energy for dimer dissociation (94 kJ/mol versus 110 kJ/mol). Quantum chemical calculations reveal the structure of the neutral and charge-resonance excited states and can rationalize the higher photodimerization quantum yield of the latter. The phenyl linker enforces close alignment of the anthracene moieties, shifting the charge resonance state to lower energy and extending the wavelength range of the photochrome while also raising the energy of the photodimer ground state to enhance the backward reaction rate. The phenyl-linked bis(anthracenes) provide a promising system to harness the [4+4] photodimerization reaction with high quantum yield, room temperature reversibility, and cyclability.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"27 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385668","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

Insight into the Thermo-responsive Phase Behavior of P1 Domain of Alpha-Synuclein using Atomistic Simulations

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-10 DOI: 10.1039/d4cp04292a

Sanchari Chakraborty, Mithun Biswas

{"title":"Insight into the Thermo-responsive Phase Behavior of P1 Domain of Alpha-Synuclein using Atomistic Simulations","authors":"Sanchari Chakraborty, Mithun Biswas","doi":"10.1039/d4cp04292a","DOIUrl":"https://doi.org/10.1039/d4cp04292a","url":null,"abstract":"Biomolecular condensate formation driven by intrinsically disordered proteins (IDPs) is regulated by interaction between various domains of the protein. Such condensates are implicated in various neurodegenerative diseases. The presynaptic intrinsically disordered protein, α -Syn is involved in the pathogenesis of Parkinson's disease. The central non-amyloid β -component (NAC) domain in the protein is considered to be a major driver of pathogenic aggregation, although recent studies have suggested that the P1 domain from the flanking N-terminal region, can act as a 'master controller' for α -Syn function and aggregation. To gain molecular insight into the phase behavior of the P1 domain itself, we investigate how assemblies of P1 (residues 36-42) chains phase separate with varying temperatures using all-atom molecular dynamics simulations. The simulations reveal that P1 is able to phase separate above a lower critical solution temperature. Formation of the condensed phase is driven by exclusion of water molecules by the hydrophobic chains. P1 chain density in the condensate is determined by weak multi-chain interactions between the residues. Moreover, Tyrosine (Y39) is involved in the formation of strongest contacts between residue pairs in the dense phase. These results provide a detailed picture of condensate formation by a key segment of the α -Syn molecule.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"18 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375238","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