Physical Chemistry Chemical Physics最新文献

{"title":"Modeling Nitric Oxide and its dimer: force field development and thermodynamics of dimerization","authors":"Tijin Saji, Thijs JH Vlugt, Sofia Calero, Behnaz Bagheri","doi":"10.1039/d5cp00784d","DOIUrl":"https://doi.org/10.1039/d5cp00784d","url":null,"abstract":"Nitric Oxide, NO, is a free radical that forms dimers, (NO)<small>₂</small>, at its vapor-liquid coexisting temperatures. In this work, we developed an all-atom force field for NO and (NO)<small>₂</small>. To assess the performance of this force field, we computed the vapor-liquid equilibrium (VLE) properties of the reactive NO-(NO)<small>₂</small> system, as well as those of pure NO and pure (NO)<small>₂</small>, using Continuous Fractional Component Monte Carlo (CFCMC) simulations. We then compared the results with the available experimental data and predictions from two previously developed force fields. For the reactive NO-(NO)<small>₂</small> system, we performed CFCMC simulations in the reactive Gibbs ensemble in which the formation of NO dimers, 2NO↔(NO)<small>₂</small>, is considered. The predicted coexistence vapor-liquid densities, dimer mole fractions in the liquid phase, saturated vapor pressures, and heats of vaporization using our force field in the temperature range 120 K to 170 K are in excellent agreement with experimental values. In addition, we conducted a systematic parameter study to analyze the sensitivity of the new force field parameters and the isolated molecule partition functions of (NO)<small>₂</small> on the VLE properties of the reactive NO-(NO)<small>₂</small> system. The results indicate that the VLE properties of the reactive NO-(NO)<small>₂</small> system are affected by both the force field parameters of the involved species as well as the isolated molecule partition functions of (NO)<small>₂</small>.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"20 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252040","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":"Photoluminescence and Self-Assembly of Three Different Eu Complexes","authors":"Adrian Ebert, Senthil Kumar Kuppusamy, Wulf Wulfhekel, Barbora Brachnakova, Peter Roesky, Mario Ruben, Lukas Gerhard, Julia Feye","doi":"10.1039/d5cp01079a","DOIUrl":"https://doi.org/10.1039/d5cp01079a","url":null,"abstract":"In this study, we investigate the photoluminescense and the self-assembly of three distinct Europium (Eu) complexes — [Eu(tta)3(bpy)](Tris(thenoyltrifluoroacetonate)europium(III)2,2’-bipyridine), [Eu(btfa)3(bpy)](Tris(4,4,4-trifluoro-1-phenyl-1,3-butanedione)europium(III)2,2’-bipyridine), and [Eu(tta)3(H2O)2](Tris(thenoyltrifluoroacetonate)europium(III) dihydrate) — on an Au(111) surface. Utilizing Scanning Tunneling Microscopy (STM), we explore the molecular topography and the ordered structures formed by these complexes, providing insight into their surface interactions. The Europium (Eu3+) ion, a member of the lanthanide series, is renowned for its unique photophysical properties, particularly its sharp emission lines and long-lived luminescence, which make it a valuable component in light-emitting devices, bio-imaging, and sensing applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"2 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252038","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":"Machine learning of the architecture-property relationship in graft polymers","authors":"Kevin V. Bigting, Jordan J. Carden, Shubhadeep Nag, Jimmy Lawrence, Yen-Fang Su, Yaxin An","doi":"10.1039/d5cp01334h","DOIUrl":"https://doi.org/10.1039/d5cp01334h","url":null,"abstract":"Bottlebrush polymers, a special class of comb polymers, are promising in energy and biomedical applications. However, the diverse architectures make it challenging to establish their structure-property relationships. We systematically investigate how backbone and side-chain architectures influence four key properties: glass transition temperature (Tg), self-diffusion coefficient (D), radius of gyration (Rg ), and packing density (ρ ). Using molecular dynamics simulations, we analyze a dataset of 500 comb polymers with randomly positioned side chains. Tg and D exhibit complicated relationships with the architectures, beyond the empirical prediction for linear polymers. To effectively capture nonlinear structure-property relationships, we develop dense neural networks (DNNs) and convolutional neural networks (CNNs).","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"7 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252037","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":"Excited-state Relaxation Mechanisms of Janus-type proton in benzimidazole-conjugated aminomaleonitrile: Single or Double Proton Transfer?","authors":"Sonika Jaglan, Sukhvinder Dhiman, Ashutosh Sharan Singh, Vijay Luxami, Gulshan Kumar","doi":"10.1039/d5cp01412c","DOIUrl":"https://doi.org/10.1039/d5cp01412c","url":null,"abstract":"The excited-state intramolecular proton transfer (ESIPT) dynamics of the ratiometric fluorescent benzimidazole-conjugated aminomalanitrile-based probe 1, an asymmetric structure synthesized by Gong et al. (RSC Adv. 2019, 9, 30943–30951), were investigated using density functional theory (DFT) and time-dependent DFT (TDDFT) methods. The presence of strengthened dual-facet hydrogen bonds in the excited state, along with charge redistribution, facilitates the ESIPT process. The geometrical optimization of six conformations identified C3 and C4 as the most stable at S₀ state (58.8% and 33.6%, respectively). Theoretical calculations align well with experimental absorption spectra and excitation values within the 350–425 nm range. FTIR analysis confirmed enhanced intramolecular hydrogen bonding (intraHBs) in C3 and C4, evidenced by redshifts and reduced interaction distances. The relative free energy profiles of tautomeric forms indicate stable states in S₀ and S₁, with low energy barriers enabling proton transfer in the excited state. The vertical emission peaks closely match experimental spectra, underscoring the role of dual-facet hydrogen bonding in photophysical behaviour. The S₁-state potential barriers suggest an excited-state single proton transfer (ESPT) rather than a double proton transfer. Upon OCl⁻ addition, the ESIPT process remains uninhibited in probe 1, confirming its OCl⁻ sensing mechanism via imidazole derivative formation. This study not only elucidates the ESIPT mechanisms of probe 1 but also enhances the understanding of HOCl detection, contributing to the development of novel fluorescent probes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"21 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252044","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":"Ni-CdS composited with ZnO for improved surface reaction and charge efficiency for photocatalytic hydrogen production from formic acid","authors":"Yanzhao Zou, Shan Yu, Shiyao Cao, Xinxin Lu, Ying Zhou","doi":"10.1039/d5cp01271f","DOIUrl":"https://doi.org/10.1039/d5cp01271f","url":null,"abstract":"Formic acid (FA) is one of ideal liquid organic hydrogen carrier (LOHC). It is of great significance to construct and design an efficient and stable photocatalytic system for H2 generation from FA decomposition. Herein, enhanced photocatalytic H2 production performance was achieved by compositing surface nickel modified cadmium sulfide (Ni-CdS) with zinc oxide. The research results indicate that the introduction of zinc oxide can not only promote the migration of photo-generated charge carriers, but also facilitate the adsorption of water molecules on the photocatalyst surface, thereby enhancing the production of hydroxyl radicals, which is a key species in the photocatalytic FA decomposition process for H2 production. Without changing the photocatalytic FA decomposition reaction pathway, Ni-CdS@ZnO-X composite material exhibits excellent photocatalytic H2 production activity and recycling stability. The H2 production activity can reach 17 mmol/g/h, which is about 2.3 times that of single cadmium sulfide material and no significant decline in photocatalytic performance going by five cycles. This study provides a new modification route for efficient and stable photocatalytic H2 production from FA decomposition under mild condition.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"135 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238204","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 insight into Cs2YZnX6 (X = Br, I) double perovskite materials for optoelectronic and thermoelectric device applications","authors":"Abid Zaman, Salhah Hamed Alrefaee, Muawya Elhadi, Pervaiz Ahmad, Mukhlisa Soliyeva, Naseem Akhter, Noureddine Elboughdiri, Vineet Tirth, Ali Algahtani, Amnah Mohammed Alsuhaibani and Moamen S. Refat","doi":"10.1039/D5CP00583C","DOIUrl":"10.1039/D5CP00583C","url":null,"abstract":"<p >In this study, we utilize first-principles calculations based on density functional theory (DFT) to examine the structural, electronic, mechanical, optical, and thermoelectric properties of Cs<small>₂</small>YZnX<small>₆</small> (X = Br, I) materials, with a focus on their potential applications in solar cells and thermoelectric devices aimed at advancing environmentally-friendly perovskite materials. The structural integrity of Cs<small>₂</small>YZnX<small>₆</small> compounds is confirmed through tolerance factor analysis, which validates their stable cubic perovskite structure. Thermodynamic stability is ensured by calculating the formation energies of both compounds. Dynamic stability is confirmed using the phonon dispersion curve. Electronic property analysis shows that both materials exhibit semiconducting behavior, with <strong>Cs<small>₂</small>YZnBr<small>₆</small></strong> having a band gap of 2.93 eV and <strong>Cs<small>₂</small>YZnI<small>₆</small></strong> having a band gap of 2.29 eV. The mechanical stability of these compounds is affirmed by the computed elastic constants, further demonstrating their suitability for practical applications. Optical property evaluation reveals that both materials have good optical absorption in the visible and UV regions, making them promising for optoelectronic applications. In addition, the thermoelectric performance of Cs<small>₂</small>YZnX<small>₆</small> is assessed, with both materials displaying a maximum Seebeck coefficient of 1.56 × 10<small>⁻³</small> V K<small>⁻¹</small> at room temperature. These findings emphasize the significant potential of Cs<small>₂</small>YZnX<small>₆</small> perovskites for integration into optoelectronic and thermoelectric devices, contributing to the advancement of sustainable materials in energy conversion technologies.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 24","pages":" 13043-13058"},"PeriodicalIF":2.9,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238229","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":"Understanding Electrochemical Reactions using Density Functional Theory: Bridging Theoretical Scheme of Squares and Experimental Cyclic Voltammetry","authors":"Amir Mahdian, Arsalan Hashemi, Kari Laasonen","doi":"10.1039/d5cp01464f","DOIUrl":"https://doi.org/10.1039/d5cp01464f","url":null,"abstract":"Mechanistic redox and acid-base reactions play pivotal roles in numerous applications in both chemistry and biology. Bridging the gap between computational insights and experimental observations is crucial to illuminate the mechanisms underlying these redox processes. In this study, we investigate electrochemical reactions by using the scheme of squares framework for a set of tens of molecules that have been examined for redox flow batteries. Furthermore, we focused on developing our computational models by calibrating the calculated redox potentials against experimental data, thereby enhancing the predictive accuracy of our approach. These findings are relevant across a wide range of applications from energy storage to medicine and synthetic chemistry.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"80 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238206","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":"Study on the mass transfer behavior of single CO2 bubbles in sodium silicate solution","authors":"Guangyan Hu, Ruoxi Zhang, Xiaomei Tang, Pengyue Sun and Taiyu Wang","doi":"10.1039/D5CP01246E","DOIUrl":"10.1039/D5CP01246E","url":null,"abstract":"<p >This study investigated in depth the mass transfer behavior of a single CO<small>₂</small> bubble in sodium silicate solution. The dynamics of the bubble were accurately tracked using high-speed camera technology, and key parameters such as velocity, drag coefficient and mass transfer coefficient during the bubble rising process were analyzed in detail with the data processing ability of MATLAB. The results showed that the concentration of sodium silicate solution had a significant impact on the dissolution behavior of the CO<small>₂</small> bubble. With the increase of concentration, the initial dissolution rate of the bubble was significantly accelerated, and the bubble in sodium silicate solution disappeared more quickly than that in deionized water. Meanwhile, an increase in liquid level would lead to a decrease of CO<small>₂</small> dissolution rate. In the study on the influence of solution pH value on CO<small>₂</small> absorption, it was found that the absorption rate at pH = 11.0 was significantly higher than that at pH = 10.5, and the whole absorption process conformed to the rapid pseudo-first-order reaction model. The kinetic parameters calculated by the model fully revealed the profound influence of solution pH value on the mass transfer and chemical reaction mechanism. Further research on the relationship between CO<small>₂</small> absorption rate and static pressure indicated that the increase of static pressure could effectively promote CO<small>₂</small> absorption in the initial stage of the reaction, and there was a significant linear positive correlation between them. However, with the progress of the reaction, due to the coupling effect of various complex factors, the deviation from linearity became pronounced with time. The absorption process could be clearly divided into the initial stage dominated by surface adsorption and preliminary reaction, the intermediate stage with accelerated absorption rate, and the later stage where the absorption rate tended to be stable. Furthermore, by comparing the liquid film mass transfer coefficients in the chemical absorption and physical absorption processes and combining with the relevant theoretical model calculations, the enhancement factor was evaluated. It reflects the enhancing effect of the chemical reaction on the mass transfer process. The empirical correlation established in this study took into account the influence of bubble size and sodium silicate concentration. The research results of this study provide a solid theoretical foundation and important data support for the process optimization of carbonization preparation of white carbon black, and have important reference value for the research and practice in related fields.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 24","pages":" 13071-13082"},"PeriodicalIF":2.9,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238209","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":"Electrochemiluminescence and conjugated polymer based photosynthesis system for regulating the photoreaction of cyanobacterium","authors":"Kai Ma, Xiukun Zhang, Pengfei Wang, Chongyu Liang, Meiting Yi, Xiaoming Sun, Zenghao Wang","doi":"10.1039/d5cp01074h","DOIUrl":"https://doi.org/10.1039/d5cp01074h","url":null,"abstract":"Photosynthesis serves as the fundamental energy conversion process sustaining life on Earth. While red and blue light spectra have been empirically utilized to enhance photosynthetic efficiency in controlled plant factories, the mechanistic interplay between these wavelengths and photochemical reactions remains underexplored. This study presents a breakthrough in photosynthetic optimization through the development of a novel tripartite system integrating cyanobacterial photochemistry (Synechococcus sp. PCC7942), an electrochemiluminescence (ECL) platform, and conjugated polymer nanoparticles (PFBT-NPs). Our engineered ECL system generates intrinsic blue emission (λ = 425 nm) through luminol oxidation, while the strategically designed PFBT-NPs enable efficient energy downconversion to red spectrum (λ = 650 nm) via Förster resonance energy transfer. Notably, the photosynthetic apparatus demonstrated that red and blue light improved the light absorption, utilization, and electron transfer in the photoreaction of Syne. The photoreaction product, such as ATP, NADPH, and NADP+ increased by 11.2%, 39.5%, and 39.3%, respectively. This work reports an ideal design of ECL system and conjugated polymer, providing a strategy to achieve simultaneous blue and red emission and promote photosynthesis.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"10 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238299","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":"Catalyst-free oxidation of nitrogen fixation by underwater bubble discharge: performance optimization and mechanism exploration","authors":"Zi-Kai Zhou, Shu-Qi Li, ChaoJun Chen, Yao Li, Xiao-Qiong Wen, De-Zheng Yang","doi":"10.1039/d5cp01500f","DOIUrl":"https://doi.org/10.1039/d5cp01500f","url":null,"abstract":"The environmental and energy challenges associated with the Haber-Bosch nitrogen fixation process present significant ecological concerns. In contrast, low-temperature plasma technology has emerged as a highly promising alternative for nitrogen fixation, capable of converting air to NOx and producing NOx- in the liquid phase using only electrical energy. In this study, nanosecond pulsed power is employed to drive an underwater microporous coaxial reactor, generating bubble spark discharges for the efficient synthesis of NOx- in water. The variation in the concentration of gas-liquid two-phase products is systematically investigated by adjusting key parameters, including pulse voltage, gas flow rate, and gas composition. Optimal nitrogen fixation is achieved at a rate of 153 µmol/min, with energy consumption as low as 4.93 MJ/mol for gas-liquid nitrogen fixation products. Results indicated that increasing the pulse voltage enhanced the NOx- yield, promoting the formation of HNO3 and NO2. However, excessive air flow rates reduced nitrogen fixation efficiency due to inadequate activation and decreased mass transfer efficiency. The addition of an optimal O2 ratio significantly improved the NOx- yield. Plasma emission spectroscopy and energy loss pathway analysis are employed to investigate the formation mechanisms of gas-phase reactive species, and potential reactions in the liquid phase are explored through modifications in reactor design. This work provides valuable insights into the regulation of gas-liquid two-phase product formation, highlighting the impact of the controlled parameters on nitrogen fixation performance.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"10 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144238203","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}