Physical Chemistry Chemical Physics最新文献_第5页

State-to-state scattering of highly vibrationally excited NO with argon at collision energies over 1 eV

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-17 DOI: 10.1039/d4cp04259j

Chatura Perera, Ethan Ross, Yang Liu, Arthur Suits, Hua Guo

{"title":"State-to-state scattering of highly vibrationally excited NO with argon at collision energies over 1 eV","authors":"Chatura Perera, Ethan Ross, Yang Liu, Arthur Suits, Hua Guo","doi":"10.1039/d4cp04259j","DOIUrl":"https://doi.org/10.1039/d4cp04259j","url":null,"abstract":"We present state-to-state differential cross sections for rotationally inelastic collisions of vibrationally excited NO X2Π (ν = 9) with Ar using a near-counterpropagating molecular beam geometry. These were obtained using the stimulated emission pumping technique coupled with velocity map imaging. Collision energies well over ~1 eV were achieved and rotational excitations up to ~ Δj = 60 recorded for the first time for inelastic collisions. This allowed us to investigate scattering of a diatomic molecule in a 2Π state which is initially well described by Hund’s case (a) into final states well described by Hund’s case (b) as the rotational level splitting becomes larger than the spin-orbit splitting. Differential cross sections for both parity-changing and parity-conserving collisions exhibit very similar structures at the high collision energies. Quantum scattering calculations have been carried out to obtain approximate integral cross sections, which confirm the high rotational excitation. These studies will take the arena of rotationally inelastic collisions to a new regime while providing insight into dynamics in extreme non-equilibrium conditions. Furthermore, these present a unique challenge to both quantum and quasiclassical scattering calculations to validate the methods and the potential energy surfaces used to assess their applicability in extreme conditions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"148 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841725","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

Viedma deracemization mechanisms in self-assembly processes 自组装过程中的维德玛脱模机制

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-17 DOI: 10.1039/d4cp03910f

Josep M. Ribó, David Hochberg, Thomas Buhse, Jean Claude Micheau

{"title":"Viedma deracemization mechanisms in self-assembly processes","authors":"Josep M. Ribó, David Hochberg, Thomas Buhse, Jean Claude Micheau","doi":"10.1039/d4cp03910f","DOIUrl":"https://doi.org/10.1039/d4cp03910f","url":null,"abstract":"Simulations on an ODE-based model shows that there are many common points between Viedma deracemization and chiral self-assemblies of achiral building blocks towards chiral nanoparticles. Both systems occur in a closed system with energy exchange but no matter exchange with the surroundings and show parallel reversible growth mechanisms which coexist with an irreversible cluster breaking (grinding). The various mechanisms of growth give rise to the formation of polymerization / depolymerization cycles while the consecutive transformation of achiral monomer into chiral cluster results into an indirect enantioselective autocatalysis. Deracemization occurs by the destabilization of the racemic non-equilibrium stationary state likely because of the excess of entropy production generated by the coupling of the reversible cluster growth mechanisms with grinding. Results show that the SMSB bias from the racemic composition occurs already at the oligomeric level of polymerization. Our model goes beyond the scope of the effect of grinding by the stirring of solutions which is thoroughly reported in supramolecular chirality. For instance, some unique characteristics, as those of a SMSB in closed systems, the simultaneous presence of different coupled reversible growth mechanisms, the activation by a depolymerization agent and the reincorporation of oligomers to the polymer growth reactions, could be adapted to replicator selectivity and to the emergence of biological homochirality scenarios.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832123","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

Enhanced phase prediction of high-entropy alloys through machine learning and data augmentation 通过机器学习和数据扩增加强高熵合金的相位预测

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-17 DOI: 10.1039/d4cp04496g

Song Wu, Zihao Song, Jianwei Wang, Xiaobin Niu, Haiyuan Chen

{"title":"Enhanced phase prediction of high-entropy alloys through machine learning and data augmentation","authors":"Song Wu, Zihao Song, Jianwei Wang, Xiaobin Niu, Haiyuan Chen","doi":"10.1039/d4cp04496g","DOIUrl":"https://doi.org/10.1039/d4cp04496g","url":null,"abstract":"The phase structure information of high-entropy alloys (HEAs) is critical for their design and application, as different phase configurations are associated with distinct chemical and physical properties. However, the broad range of elements in HEAs presents significant challenges for precise experimental design and rational theoretical modeling and simulation. To address these challenges, machine learning (ML) methods have emerged as powerful tools for phase structure prediction. In this study, we use a dataset of 544 HEA configurations to predict phases, including 248 intermetallic, 131 solid solution, and 165 amorphous phases. To mitigate the limitations imposed by the small dataset size, we employ a Generative Adversarial Network (GAN) to augment the existing data. Our results show a significant improvement in model performance with data augmentation, achieving an average accuracy of 94.77% across ten random seeds. Validation on an independent dataset confirms the model's reliability and real-world applicability, achieving 100% prediction accuracy. We also predict FCC and BCC phases for SS HEAs based on elemental composition, achieving a peak accuracy of 98%. Furthermore, feature importance analysis identifies correlations between compositional features and phase formation tendencies, which are consistent with experimental observations. This work proposes an effective strategy to enhance the accuracy and generalizability of machine learning models in phase structure prediction, thus promoting the accelerated design of HEAs for a wide range of applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"38 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832121","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

Ferroelastic Phase Transition-Modulated Electronic Transport and Photoelectric Properties in Monolayer 1T' ZrCl₂ 单层 1T' ZrCl₂ 中的铁弹性相变调制电子传输和光电特性

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-17 DOI: 10.1039/d4cp04315d

Yuehua Xu, He Sun, Jindian Chen, Qianqian Long, Haowen Xu

{"title":"Ferroelastic Phase Transition-Modulated Electronic Transport and Photoelectric Properties in Monolayer 1T' ZrCl₂","authors":"Yuehua Xu, He Sun, Jindian Chen, Qianqian Long, Haowen Xu","doi":"10.1039/d4cp04315d","DOIUrl":"https://doi.org/10.1039/d4cp04315d","url":null,"abstract":"Monolayer 1T' ZrCl₂ exhibits unique ferroelastic behavior with three structurally distinct variants (O1, O2, and O3), offering the potential for next-generation nanoelectronic and optoelectronic devices. This study investigates the electronic transport and optoelectronic properties of the O1 and O3 variants, with O3 serving as a representative for both O2 and O3 due to their structural symmetry. First-principles calculations and non-equilibrium Green's function analysis reveal that the O1 variant possesses exceptional electronic properties, including high electron mobility (1.44×10⁴ cm²/V·s) and a large current on/off ratio (10⁶), while the O3 variant shows high conductivity in both crystallographic directions. Optoelectronically, the O1 variant demonstrates strong anisotropy with a maximum photocurrent density of 6.57 μA/mm², photo responsivity of 0.37 A/W, and external quantum efficiency of 41.08% along the a direction, outperforming many 2D materials, whereas there is negligible response along the b direction. In contrast, the O3 variant exhibits a more balanced photoresponse with comparable performance in both directions. These findings provide insights into structure-property relationships in ferroelastic 2D materials and pave the way for developing phase transition-based multifunctional devices for applications in information processing, energy conversion, and sensing.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"47 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832119","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

Length-dependent water permeation through a graphene channel

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-17 DOI: 10.1039/d4cp03920c

Zi Wang, Shuang Li, Shiwu Gao, Jiaye Su

{"title":"Length-dependent water permeation through a graphene channel","authors":"Zi Wang, Shuang Li, Shiwu Gao, Jiaye Su","doi":"10.1039/d4cp03920c","DOIUrl":"https://doi.org/10.1039/d4cp03920c","url":null,"abstract":"Water confined in two-dimensional channels exhibits unique properties, such as rich morphology, specific phase transition and a low dielectric constant. In this work, molecular dynamics simulations have been used to study the water transport in two-dimensional graphene channels. The structures and dynamics of water under confinement show strong dependence on the channel length and thickness of the channels. In particular, there exists a critical channel length beyond which monolayer water forms square-like ice structures, leading to the rapid decrease in water flow that eventually ceases completely. The water flow for double-layer and three-layer systems exhibits a similar exponential decay but does not reach zero. The translocation time exhibits an excellent power-law behavior with an increase in the channel length, accounting for the exponential flow decay. The radial distribution function confirms the length-dependent liquid-to-ice phase transition of monolayer water and the liquid states for double-layer and three-layer systems. The formation of monolayer ice can be further supported by the increasing barriers in the potential of mean force and specific dipole distributions. Furthermore, the melting temperature of monolayer ice increases significantly with the increase in the channel length that can also be close to or even exceeds the boiling point at atmospheric pressure. These findings provide new physical insights into the extraordinary length-dependent water behaviors and suggest future experimental studies on high-temperature ice through the size control in nanochannels.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"25 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832122","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

Deep Learning-Driven Prediction of Chemical Addition Patterns for Carboncones and Fullerenes 深度学习驱动的碳锥和富勒烯化学加成模式预测

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-17 DOI: 10.1039/d4cp03238a

Zhengda Li, Xuyang Chen, Yang Wang

{"title":"Deep Learning-Driven Prediction of Chemical Addition Patterns for Carboncones and Fullerenes","authors":"Zhengda Li, Xuyang Chen, Yang Wang","doi":"10.1039/d4cp03238a","DOIUrl":"https://doi.org/10.1039/d4cp03238a","url":null,"abstract":"Carboncones and fullerenes are exemplary π-conjugated carbon nanomaterials with unsaturated, positively curved surfaces, enabling the attachment of atoms or functional groups to enhance their physicochemical properties. However, predicting and understanding the addition patterns in functionalized carboncones and fullerenes are extremely challenging due to the formidable complexity of the regioselectivity exhibited in the adducts. Existing predictive models fall short in systems where the carbon molecular framework undergoes severe distortion upon high degrees of addition. Here, we propose an incremental deep learning approach to predict regioselectivity in the hydrogenation of carboncones and chlorination of fullerenes. Utilizing exclusively graph-based features, our deep neural network (DNN) models rely solely on atomic connectivity, without requiring 3D molecular coordinates as input or iterative optimization of them. This advantage inherently avoids the risk of obtaining chemically unreasonable optimized structures, enabling the handling of highly distorted adducts. The DNN models allow us to study regioselectivity in hydrogenated carboncones of C70H20 and C62H16, accommodating up to at least, 40 and 30 additional H atoms, respectively. Our approach also correctly predicts experimental addition patterns in C50Cl10 and C76Cln (n = 18, 24, and 28), whereas in the latter cases all other known methods have proven unsuccessful. Compared to our previously developed topology-based models, the DNN’s superior predictive power and generalization ability make it a promising tool for investigating complex addition patterns in similar chemical systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"10 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832124","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

Self-assembly of cationic surfactant in choline chloride-based deep eutectic solvents: structural solvation and dynamics 阳离子表面活性剂在氯化胆碱深共晶溶剂中的自组装：结构溶解和动力学

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-17 DOI: 10.1039/d4cp02739f

Yagnik Vora, Omish Sethi, Sanjay N. Bariya, Santosh L. Gawali, Saurabh S. Soni, Tejwant Singh Kang, Puthusserickal A. Hassan, Ketan Kuperkar

{"title":"Self-assembly of cationic surfactant in choline chloride-based deep eutectic solvents: structural solvation and dynamics","authors":"Yagnik Vora, Omish Sethi, Sanjay N. Bariya, Santosh L. Gawali, Saurabh S. Soni, Tejwant Singh Kang, Puthusserickal A. Hassan, Ketan Kuperkar","doi":"10.1039/d4cp02739f","DOIUrl":"https://doi.org/10.1039/d4cp02739f","url":null,"abstract":"Deep eutectic solvents (DESs) have gained popularity in various applications due to their improved environmental sustainability and biodegradability. For the present study, several polyhydric alcohols, including ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), and glycerol (Gly), have been used as hydrogen bond donors (HBDs) and choline chloride (ChCl) as a hydrogen bond acceptor (HBA) in a fixed molar ratio to form a homogenous and stable DES. Controlled water mixing into such neat DESs has always been thought to be a quick and efficient method to tune the chemical and thermodynamic properties of DESs. The structural solvation and dynamics of the prepared DESs with the inclusion of water vary from low to high water concentrations that have been examined employing Fourier transform infrared (FT-IR), and proton nuclear magnetic resonance (1H-NMR) spectroscopy. Herein, the micellization behavior of a cationic surfactant, dodecyltrimethylammonium bromide (DTAB), in neat DESs and DES–water mixtures has been demonstrated by using tensiometry, dynamic light scattering (DLS), and small-angle X-ray scattering (SAXS) techniques. Furthermore, it has been observed that DESs exhibit an ample thermodynamic driving force for creating micelles, since they contain an H-bonded nanostructure. However, such self-assembly appears to be very much dependent on DESs, the amount of water, and the surfactant used. A computational simulation approach using a semiempirical method is put forth employing the Gaussian 09 W calculation window in the Gauss View 5.0.9 software package. In addition, this study includes the determination of several optimized descriptors that intend to offer an in-depth examination of the surfactant–DES interactions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"41 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832204","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

Experimental and computational studies of novel cationic Gemini surfactant as corrosion inhibitors for carbon steel in 15% HCl

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-16 DOI: 10.1039/d4cp03616f

Chenxu Wang, Erlong Yang

{"title":"Experimental and computational studies of novel cationic Gemini surfactant as corrosion inhibitors for carbon steel in 15% HCl","authors":"Chenxu Wang, Erlong Yang","doi":"10.1039/d4cp03616f","DOIUrl":"https://doi.org/10.1039/d4cp03616f","url":null,"abstract":"In the process of oil and gas exploration, the corrosion of carbon steel pipes leads to substantial economic losses, numerous casualties, environmental contamination, and resource waste. The advancement of highly efficient and stable corrosion inhibitors holds significant importance for protecting carbon steel from corrosion during oil and gas exploitation. In this study, two new cationic Gemini surfactants (2CncoesT, where n = 12, 14) were synthesized through a straightforward two-step reaction. Weight-loss tests demonstrated that the inhibition efficiency (ηw%) increases with the temperature rise. Specifically, the maximum ηw% values for 2C12coesT and 2C14coesT attained 97.97% and 98.27% respectively at 85℃. The adsorption of these surfactants conformed to the Langmuir adsorption isotherm. Electrochemical measurements suggested that the two surfactants functioned as mixed-type inhibitors. The findings obtained from the scanning electron microscope (SEM) were consistent with the experimental outcomes that 2C12coesT and 2C14coesT are efficient inhibitors for the metal in an acidic environment. The quantum chemical investigation and Molecular dynamics simulation(MD) further substantiated the experimental results and offered insights for a deeper comprehension of the inhibition mechanism of Gemini surfactants.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"253 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142825715","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

Assembly of graphene oxide vs. reduced graphene oxide in a phospholipid monolayer at air-water interface 氧化石墨烯与还原氧化石墨烯在空气-水界面磷脂单层中的组装

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-16 DOI: 10.1039/d4cp02706j

Ajit Seth, Priya Mandal, Prashant Hitaishi, Rajendra P. Giri, Bridget Mary Murphy, Sajal Kumar Ghosh

{"title":"Assembly of graphene oxide vs. reduced graphene oxide in a phospholipid monolayer at air-water interface","authors":"Ajit Seth, Priya Mandal, Prashant Hitaishi, Rajendra P. Giri, Bridget Mary Murphy, Sajal Kumar Ghosh","doi":"10.1039/d4cp02706j","DOIUrl":"https://doi.org/10.1039/d4cp02706j","url":null,"abstract":"Graphene and its derivatives, such as graphene oxide (GO) and reduced graphene oxide (rGO), have propelled advancements in biosensor research owing to their unique physicochemical and electronic characteristics. To ensure their safe and effective utilization in biological environments, it is crucial to understand how these graphene-based nanomaterials (GNMs) interact with a biological milieu. The present study depicts GNMs-induced structural changes in a self-assembled phospholipid monolayer formed at an air water interface that can be-considered to represent one of the leaflets of a cellular membrane. Surface pressure-area isotherm and electrostatic surface potential measurements, along with advanced X-ray scattering techniques, have been utilized in this study. Experimental findings demonstrate a strong interaction between negatively charged GO flakes and a positively charged monolayer, primarily dictated by electrostatic forces. These GO flakes assemble horizontally beneath the head groups of the monolayer. On the contrary, rGO flakes permeate the zwitterionic lipid layer through dominant hydrophobic interaction. This organization of GNMs alters the in-plane elasticity of the lipid film, exhibiting a drop in the electrostatic potential of the surface according to the extent of oxygen-containing groups. These results provide a solid groundwork for designing devices and sensors aimed at augmenting the biomedical applications of GNMs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"38 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832126","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

An Experimental and Computational Kinetic Evaluation of Silver (I)-Catalyzed Oxidation of p-Chlorophenol by Hexacyanoferrate (III): Exploring the Mechanistic Pathway 六氰合铁(III)催化银(I)氧化对氯苯酚的实验和计算动力学评估：机理途径探索

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2024-12-16 DOI: 10.1039/d4cp02495h

Asha Rolaniya, Akta Yadav, Priyanka Jain, Riya Sailani

{"title":"An Experimental and Computational Kinetic Evaluation of Silver (I)-Catalyzed Oxidation of p-Chlorophenol by Hexacyanoferrate (III): Exploring the Mechanistic Pathway","authors":"Asha Rolaniya, Akta Yadav, Priyanka Jain, Riya Sailani","doi":"10.1039/d4cp02495h","DOIUrl":"https://doi.org/10.1039/d4cp02495h","url":null,"abstract":"The present investigation delves into the redox reaction between p-chlorophenol (p-CP) and hexacyanoferrate (III) [HCF (III)], catalyzed by Ag (I) within an alkaline environment. Findings reveal a first-order dependence on both p-CP and the oxidant, also the reaction rate showcases a first-order respect towards Ag (I), further amplified by the medium as per the equation kobs = a + b[OH-]. Interestingly, the ionic strength remains unchanged throughout the reaction, exerting no discernible effect on the reaction rate. Evaluation of activation and thermodynamic parameters utilizes the Arrhenius and Eyring equations. Spectral analysis identifies the oxidation product of p-CP as hydroquinone. Exploration extends to various organic solvents, with their effects scrutinized through Taft's and Swain's multiparametric equations. Notably, the rate constants fall to correlate satisfactorily with Kamlet-Taft's solvatochromic parameters (α, β, π*). Building upon kinetic findings, a plausible reaction mechanism is proposed. This proposition gains substantial reinforcement from additional evidence derived through Density Functional Theory (DFT) computations conducted at the b3lyp/6-311*g (d,p) level. These computations reveal activation energy barriers consistent with observed reactivity trends in kinetics experiments, thereby solidifying support for the proposed mechanism.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832125","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