Physical Chemistry Chemical Physics最新文献

{"title":"Novel Cs2AuIMIIIF6 (M = As, Sb) double halide perovskites: sunlight and industrial waste heat management device applications","authors":"Shuaib Mahmud, Usama Ahmed, Md. Atik Uz Zaman Atik, Md. Mukter Hossain, Md. Mohi Uddin, Md. Ashraf Ali","doi":"10.1039/d4cp04293j","DOIUrl":"https://doi.org/10.1039/d4cp04293j","url":null,"abstract":"The upcoming lead-free double halide perovskites are sustainable alternatives to lead perovskites in renewable energy technologies. This study conducted a comprehensive investigation into the structural, electronic, optical, and thermoelectric properties of novel Cs<small>₂</small>Au<small>^I</small>M<small>^III</small>F<small>₆</small> (M = As, Sb) double halide perovskites using a density functional theory-based approach. The tolerance factors and negative formation energies, as well as analysis of phonon dispersion, confirm structural and dynamic stability. There are favorable values of elastic coefficients and Pugh's and Poisson's ratios, which prove that there is mechanical stability, and ductility is also proven. The compounds show indirect band gaps of 1.144 eV (Cs<small>₂</small>AuAsF<small>₆</small>) and 1.746 eV (Cs<small>₂</small>AuSbF<small>₆</small>), which fall within the range of absorption of visible light. Optical analysis reveals high absorption coefficients, thereby making this material suitable for photovoltaic applications. Thermoelectric properties show moderate <em>ZT</em> values of approximately 0.64 and 0.61 at 500 K, which signify their application for waste heat recovery. Thus, the currently presented work proves the potential of Cs<small>₂</small>Au<small>^I</small>M<small>^III</small>F<small>₆</small> (M = As, Sb) perovskites as effective materials from an environmental perspective for energy harvesting devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"41 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393727","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":"Anharmonicity and Vibrational Stark Fields in Phosphinic Acid Dimers","authors":"B. Manjusha, Arzoo Arzoo, G. Naresh Patwari","doi":"10.1039/d4cp03394a","DOIUrl":"https://doi.org/10.1039/d4cp03394a","url":null,"abstract":"Phosphinic acid is unique among oxyacids of phosphorus with the ability to form cyclic dimers via intermolecular hydrogen bonding, analogous to carboxylic acid dimers with exceptional stability and higher dimerization enthalpies due to stronger hydrogen bonding interactions. The strength of the hydrogen bond with different combinations of substituents on the monomeric units can be effectively studied by evaluation of electric fields along the hydrogen-bonded OH donor groups. The correlation between OH stretch vibrational frequency and electric field was linear with average stark tuning rates of 45.6 and 11.8 cm-1(MV cm-1)-1 respectively for the primary and secondary substitution effects, which by comparison is more than double relative to carboxylic acid dimers. Further, the Stark tuning rate for the anharmonic O–D frequency shifts on average was about 40-50% higher compared to the corresponding harmonic O–D frequency shifts, which suggests the presence of strong anharmonicity of O–H/O–D oscillators in phosphinic acid dimers.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"30 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393732","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":"First Principles Assessment of Solvent Induced Cage Effects on Intramolecular Hydrogen Transfer in the Free Radical Polymerization of Acrylates","authors":"Francesco Serse, Matteo Salvalaglio, Matteo Pelucchi","doi":"10.1039/d4cp04415k","DOIUrl":"https://doi.org/10.1039/d4cp04415k","url":null,"abstract":"We investigate the rate constant of poly-butyl acrylate backbiting between 310 and 510 K using semi-empirical metadynamics in the gas phase, bulk and solution. The simulations in condensed phase are performed through a hybrid quantum mechanics/molecular mechanics approach. The free energy landscape associated to the reactive events in vacuum and in condesed phase are used to correct harmonic transition state theory (TST) rate constants. The Arrhenius parameters so determined are introduced in a semi-detailed mechanistic kinetic mechanism of butyl acrylate polymerization in bulk and in solution, allowing to test how butyl acrylate polymerization rate is affected by solvent-induced cage effects on backbiting. The results show that the backbiting rate constant is higher in the condensed phase than in the gas phase. In addition, a twofold increase is observed in xylene compared to bulk. These results differ significantly from previous theoretical calculations, especially at high temperatures, aligning better with experimental rate measurements. The semi-detailed model, incorporating our calculated rate coefficients, is validated against monomer concentration profiles from bulk and solution polymerizations in various reactor configurations, demonstrating good agreement with experimental data. This study paves the way for developing detailed kinetic models in the condensed phase using a priori kinetic parameters derived from molecular simulations, thus widening their range of applicability beyond the one experimentally accessible.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"10 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393978","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":"Single-Chirality Single-Wall Carbon Nanotubes for Electrochemical Biosensing","authors":"Ju-Yeon Seo, Bahar Mostafiz, Xiaomin Tu, Constantine Yuri Khripin, Ming Zheng, Han Li, Emilia Peltola","doi":"10.1039/d4cp04206a","DOIUrl":"https://doi.org/10.1039/d4cp04206a","url":null,"abstract":"Single-wall carbon nanotubes (SWCNTs) exhibit versatile optoelectronic properties closely linked to their structural characteristics, such as chiral angles and diameters. Given this, they are promising materials for biosensors. However, in studies investigating SWCNT-based electrochemical biosensors, raw soot has been mostly used. Soot typically contains a mixture of different chiralities, metallic compounds, and various impurities from the synthesis process. As a result, this mixture significantly limits the reproducibility and precision of SWCNT-based sensors. To ensure consistent sensor performance, we employed an aqueous two-phase extraction technique to purify and sort single-chirality SWCNTs—specifically, semiconducting (6,5) SWCNTs and metallic (6,6) SWCNTs. In addition, we used multiple fabrication methods to ensure that only pure-chirality SWCNTs were deposited onto the electrodes. Our findings emphasise the importance of using surfactant-free systems when investigating the influence of chirality on the electrochemical behaviour of SWCNTs. By using monochiral SWCNTs, we achieved precise control over their concentration and density, allowing us to assess their electrochemical properties accurately. Our results reveal that the adsorption-controlled process of the inner sphere redox probe (ISR) occurs on (6,5) SWCNTs, while a diffusion-controlled process is observed on (6,6) SWCNTs. These findings provide valuable insights that will enhance the performance of SWCNTs-based electrochemical biosensors.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"60 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385604","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":"Proton Transport in Liquid Phosphoric Acid: The Role of Nuclear Quantum Effects Revealed by Neural Network Potential","authors":"Pei Liu, Wei Li, Shuhua Li","doi":"10.1039/d4cp04195j","DOIUrl":"https://doi.org/10.1039/d4cp04195j","url":null,"abstract":"Pure phosphoric acid exhibits high proton conductivity and is widely used in modern industry. However, its proton transport (PT) mechanism remains less understood compared to that of water, which presents a significant challenge for advancing technologies like phosphoric acid fuel cells. In this study, we utilize machine learning (ML) potentials and molecular dynamics (MD) simulations to investigate the proton diffusion mechanisms in liquid phosphoric acid systems. The neural network potentials (NNPs) we developed demonstrate quantum chemical accuracy and stability across a range of temperatures. Our simulations reveal continuous proton hopping between phosphoric acid anions. Moreover, the radial distribution functions (RDFs) and diffusion coefficients obtained from ring polymer MD (RPMD)—a variant of path-integral MD (PIMD)—exhibit improved alignment with experimental values compared to classical MD results, as RPMD inherently accounts for nuclear quantum effects (NQEs) on proton behavior. Additionally, we employed neural networks (NN) combined with the charge equilibration method to predict the charge distribution in liquid phosphoric acid, examining the PT mechanism through vibrational spectra analysis. These findings provide deeper insights into the high proton conductivity of liquid phosphoric acid.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385665","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 new approach to a first order irreversible homogeneous chemical reaction followed by an electrochemical process: theory, simulation and application","authors":"Rafael Alessandro Lima Chioquetti, Raphael Prata Bacil, Silvia Serrano","doi":"10.1039/d4cp04092a","DOIUrl":"https://doi.org/10.1039/d4cp04092a","url":null,"abstract":"Chronoamperometric profiles were derived for systems in which an irreversible, homogeneous chemical reaction generates an electroactive species that readily reacts at the surface of a planar electrode. From the resulting current (i) equations, a convolution approach was proposed to extract the rate constant of the chemical reaction through non-linear fitting. These equations were validated using digital simulations, and the semi-derivative approach successfully recovered the simulated parameters. The proposed kinetic method was then applied experimentally to the chemical oxidation of iodide by hydrogen peroxide in acidic medium, followed by the electrochemical reduction of triiodide. The rate constants measured with this kinetic method were consistent with existing literature across various temperatures, and an Arrhenius plot led to a reasonable value for an activation energy of the process.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"4 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385667","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":"Ferrocene derivatives and aniline copolymers with tunable magnetoresistance and dielectric properties","authors":"Huiyan Ren, Hongbo Gu","doi":"10.1039/d4cp04612a","DOIUrl":"https://doi.org/10.1039/d4cp04612a","url":null,"abstract":"Inspired by the electron-rich characteristics of ferrocene (Fc), we have strategically integrated this compound into polyaniline (PANI), aiming to modulate the magnetoresistance (MR) and dielectric properties of PANI. The copolymers (P(ANI-co-FcA)) were synthesized by copolymerization of aniline and 1,1’-bis[(4-aminophenyl)amino]carbon]ferrocene (FcA). The resistivity and temperature-dependent resistivity are performed to unveil the charge carrier transport mechanism, aligning with the Efros-Shklovskii variable-range hopping (ES-VRH) model. Additionally, the MR and dielectric properties are tuned by alternating the FcA content in the main chain of copolymers. MR analysis reveals a positive effect, which is intensified with an increased FcA content. Notably, the MR effect of P(ANI-co-FcA)-3 attains 1.51% under a magnetic field of 3 T. The real permittivity of copolymers is changed from negative to positive values upon the incorporation of FcA. This research proffers an approach to manipulating the electrical performance of conducting polymer materials for potential applications in electronic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"10 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385605","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":"Correction: Symmetry-breaking charge transfer and intersystem crossing in copper phthalocyanine thin films","authors":"Esther del Pino Rosendo, Okan Yildiz, Wojciech Pisula, Tomasz Marszalek, Paul W. M. Blom and Charusheela Ramanan","doi":"10.1039/D5CP90033F","DOIUrl":"10.1039/D5CP90033F","url":null,"abstract":"<p >Correction for ‘Symmetry-breaking charge transfer and intersystem crossing in copper phthalocyanine thin films’ by Esther del Pino Rosendo <em>et al.</em>, <em>Phys. Chem. Chem. Phys.</em>, 2023, <strong>25</strong>, 6847–6856, https://doi.org/10.1039/D2CP05240G.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 8","pages":" 4495-4495"},"PeriodicalIF":2.9,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cp/d5cp90033f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385666","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":"On the Stability Constants of Metal-Nitrate Complexes in Aqueous Solutions","authors":"Mohammadhasan (Hadi) Dinpajooh, Greta L Hightower, Richard E Overstreet, Lori A Metz, Neil Henson, Niranjan Govind, Andrew Ritzmann, Nicolas E Uhnak","doi":"10.1039/d4cp04295f","DOIUrl":"https://doi.org/10.1039/d4cp04295f","url":null,"abstract":"Stability constants of simple reactions involving addition of the NO<small>₃</small><small>^-</small> ion to hydrated metal complexes, [M(H<small>₂</small>O)<small>_x</small>]<small>ⁿ⁺</small> are calculated with a computational workflow developed using cloud computing resources. The computational workflow performs conformational searches for metal complexes at both low and high levels of theories in conjunction with a continuum solvation model (CSM). The low-level theory is mainly used for the initial conformational searches, which are complemented with high-level density functional theory conformational searches in the CSM framework to determine the coordination chemistry relevant for stability constant calculations. In this regard, the lowest energy conformations are found to obtain the reaction free energies for the addition of one NO<small>₃</small><small>^-</small> to [M(H<small>₂</small>O)<small>_x</small>]<small>ⁿ⁺</small> complexes, where M represents Fe(II), Fe(III), Sr(II), Ce(III), Ce(IV), and U(VI), respectively. Structural analysis of hundreds of optimized geometries at high-level theory reveals that NO<small>₃</small><small>^-</small> coordinates with Fe(II) and Fe(III) in either a monodentate or bidentate manner. Interestingly, the lowest-energy conformations of Fe(II) metal-nitrate complexes exhibit monodentate or bidentate coordination with a coordination number of 6 while the bidentate seven-coordinated Fe(II) metal-nitrate complexes are approximately 2 kcal/mol higher in energy. Notably, for Fe(III) metal-nitrate complexes, the bidentate seven-coordinated configuration is more stable than the six-coordinated Fe(II) complexes (monodentate or bidentate) by a few thermal energy units. In contrast, Sr(II), Ce(III), Ce(IV), and U(VI) metal ions predominantly coordinate with NO<small>₃</small><small>^-</small> in a bidentate manner, exhibiting typical coordination numbers of 7, 9, 9, and 5, respectively. Stability constants are accordingly calculated using linear free energy approaches to account for the systematic errors and good agreements are obtained between the calculated stability constants and the available experimental data.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"17 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385670","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":"Self-powered photodetector of GaN/Sc2CCl2 heterojunction with high carrier mobility and polarization sensitivity","authors":"Guoqing Zhang, Zhen Cui, Aming Song, Shuang Zhang, Lu Wang","doi":"10.1039/d4cp04162c","DOIUrl":"https://doi.org/10.1039/d4cp04162c","url":null,"abstract":"This study is based on first-principles calculations to investigate the GaN/Sc<small>₂</small>CCl<small>₂</small> heterojunction, and its electrical properties, optical properties, and photogalvanic effect under linearly polarized light are calculated. The GaN/Sc<small>₂</small>CCl<small>₂</small> heterojunction is a narrow-bandgap semiconductor (1.15 eV) with excellent dynamic and thermal stability, featuring electron transfer from the GaN layer to the Sc<small>₂</small>CCl<small>₂</small> layer. The heterojunction exhibits high carrier mobility (5670 cm<small>²</small> V<small>⁻¹</small> s<small>⁻¹</small>) and significantly enhanced light absorption in the visible spectrum compared to its monolayer counterparts. For the GaN/Sc<small>₂</small>CCl<small>₂</small> self-powered photodetector, the photocurrent shows little variation between linearly and elliptically polarized light, indicating low sensitivity to polarization type. Notably, at a photon energy of 1.2 eV, the photocurrent and extinction ratio reach maximum values of 12.78 <em>a</em><small>₀</small><small>²</small> per photon and 326.1, respectively, demonstrating excellent photoresponse and high polarization sensitivity. The GaN/Sc<small>₂</small>CCl<small>₂</small> heterojunction can be used as an efficient photodetector material in fields such as photodetection. This research provides an effective strategy for designing high-performance heterojunction photodetectors.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"47 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375233","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}