Physical Chemistry Chemical Physics最新文献

{"title":"Quantum chemical and kinetic study of the reaction between CCl2 and NO2 radicals","authors":"Nicolás Damián Gómez, María Paula Badenes, Maria Eugenia Tucceri, Carlos J Cobos","doi":"10.1039/d4cp03168g","DOIUrl":"https://doi.org/10.1039/d4cp03168g","url":null,"abstract":"The dependence of the rate constant of the recombination reaction of CCl<small>₂</small> and NO<small>₂</small> radicals on temperature and pressure was studied. Quantum-chemical calculations were employed to characterize relevant aspects of the potential energy surface for this process. The limiting rate constants between 300 and 2000 K were analyzed using the unimolecular reactions theory. The resulting low pressure rate constant can be represented as <em>k</em><small>₀</small> = [He] (1.4 ± 0.2) x 10<small>^-26</small> (T/300 K)<small>^{(-8.72±0.04)}</small>exp(-(1520 ± 10) K/T) cm<small>³</small> molecule<small>^-1</small> s<small>^-1</small>. The corresponding expressions for the high pressure limit rate constants, derived from a simplified version of the statistical adiabatic channel (SSACM) and from a SACM combined with classical trajectory calculations (SACM/CT), are (2.3 ± 1.9) x 10<small>^-11</small> (T/300 K)<small>^{(-1.01±0.39)}</small>exp(-(810 ± 80) K/T) and (8.8 ± 5.3) x 10<small>^-13</small> (T/300 K)<small>^(0.82±0.13)</small> cm<small>³</small> molecule<small>^-1</small> s<small>^-1</small>. The falloff curves were represented in terms of these limiting rate constants. Reported experimental results are well described with the present model. Our calculations indicate that the CCl<small>₂</small> + NO<small>₂</small> reaction proceeds via the stabilization of the energized CCl<small>₂</small>NO<small>₂</small> adduct, and that the CCl<small>₂</small> + NO<small>₂</small> → CCl<small>₂</small>O + NO channel becomes relevant at high temperatures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"26 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879833","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":"Thermodynamics and models for small nanoparticles upon protein adsorption","authors":"Miao-Miao Yin, Yi-Bo Yuan, Xin Ding, Yan-Jun Hu, Feng-Lei Jiang","doi":"10.1039/d4cp03518f","DOIUrl":"https://doi.org/10.1039/d4cp03518f","url":null,"abstract":"Proteins are some of the most important components in living organisms. When nanoparticles enter a living system, they swiftly interact with proteins to produce the so-called “protein corona”, which depicts the adsorption of proteins on large nanoparticles (normally tens to hundreds of nanometers). However, the sizes of small nanoparticles (typically, fluorescent nanomaterials such as quantum dots, noble metal nanoclusters, carbon dots, <em>etc.</em>) are less than 10 nm, which are comparable or even much smaller than those of proteins. Can proteins also adsorb onto the surface of small nanoparticles to form a “protein corona”? In this perspective, the interactions between small nanoparticles with proteins are discussed in detail, including the main characterization methods and thermodynamic mechanisms. The interaction models are summarized. In particular, the concept of a “protein complex” is emphasized.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"22 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879839","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":"Ultrahigh carrier mobility and multidirectional piezoelectricity in 2D Janus copper-containing chalcogenides monolayers","authors":"Mengbing Liu, Xingxu Meng, Yuli Yan, Huabing Yin","doi":"10.1039/d4cp04128c","DOIUrl":"https://doi.org/10.1039/d4cp04128c","url":null,"abstract":"Two-dimensional (2D) materials have attracted enormous research attention due to their remarkable properties and potential applications in electronic and optoelectronic devices. In this work, the Janus 2D copper-containing chalcogenides, CuP<small>₂</small>Se<small>_0.5</small>S<small>_0.5</small> and CuP<small>₂</small>Te<small>_0.5</small>Se<small>_0.5</small> monolayers, are proposed and studied systematically based on first-principles calculations. These two Janus-structured materials possess the same thermal and dynamic stability as the perfect CuP<small>₂</small>Se structure. Remarkably, we observe multiple VBM and CBM points with negligible energy differences in the band structures of perfect CuP<small>₂</small>Se and Janus CuP<small>₂</small>Se<small>_0.5</small>S<small>_0.5</small> and CuP<small>₂</small>Te<small>_0.5</small>Se<small>_0.5</small> monolayers. This will significantly impact the electronic and transport properties of the material. The calculated anisotropic carrier mobilities can reach 10<small>⁴</small>∼10<small>⁵</small> cm<small>²</small> V<small>⁻¹</small> s<small>⁻¹</small> orders of magnitude, which are higher than those of most reported materials. Meanwhile, the two Janus derivatives, CuP<small>₂</small>Se<small>_0.5</small>S<small>_0.5</small> and CuP<small>₂</small>Te<small>_0.5</small>Se<small>_0.5</small> monolayers, exhibit outstanding multidirectional piezoelectricity, which are comparable with those of traditional piezoelectric materials. The combination of ultrahigh carrier mobility and multidirectional piezoelectricity indicates that these novel 2D Janus materials could be promising for applications in electronic and piezoelectric devices under special conditions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"34 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879835","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":"Templated Self-Organization of Polymer-Tethered Gold Nanoparticles into Freestanding Superlattices at Liquid-Air Interface","authors":"Ye Gao, Lingli Wan, Yuqing Song, Shan Gao, Nan Yan, Fan Wu, Yanqiu Du","doi":"10.1039/d4cp04435e","DOIUrl":"https://doi.org/10.1039/d4cp04435e","url":null,"abstract":"Programmable organization of uniform organic/inorganic functional building blocks into large-scale ordered superlattices has attracted considerable attention since the bottom-up self-organization strategy opens up a robust and universal route for designing novel and multifunctional materials with advanced applications in memory storage devices, catalysis, photonic crystals, and biotherapy. Despite great efforts have been made in the construction of the superlattice materials, there still remains a challenge in the preparation of organic/inorganic hybrid superlattices with tunable dimensions and exotic configurations. Here, we report the spontaneous self-organization of polystyrene-tethered gold nanoparticles (AuNPs@PS) into freestanding organic/inorganic hybrid superlattices templated by the diethylene glycol-air interface. The resulting multilayer 3D superlattices exhibit hexagonally honeycomb and periodically tetrahedral lattice after the evaporation of AuNPs@PS building blocks at the liquid-air interface. Notably, a particular Moiré pattern originating from the twisted stacking of the adjacent layers is observed when the twist angle is 30°, leading to the exquisite quasi-crystalline packing with 12-fold rotational symmetry. In addition, the interparticle distance and gap within the 2D superlattice can be precisely regulated by adjusting the length of polymer segments, thereby generating the distinctive 3D graphene-skeleton configurations in the freestanding superlattice. This finding presents a highly efficient and versatile way to artificially produce multifunctional organic/inorganic hybrid superlattice materials with adjustable dimensions and internal configurations.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"113 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879907","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":"Ion pairing in aqueous tetramethylammonium--acetate solutions by neutron scattering and molecular dynamics simulations","authors":"Ngoc Lan Le Nguyen, Ondrej Tichacek, Pavel Jungwirth, Hector Martinez-Seara, Phil Mason, Elise Duboué-Dijon","doi":"10.1039/d4cp04312j","DOIUrl":"https://doi.org/10.1039/d4cp04312j","url":null,"abstract":"Tetramethylammonium (TMA) is a ubiquitous cationic motif in biochemistry, found in the charged choline headgroup of membrane phospholipids and in trimethylated lysine residues, which modulate histone-DNA interactions and impact epigenetic mechanisms. TMA interactions with anionic species, particularly carboxylate groups of amino acid residues and extracellular sugars, are of substantial biological relevance, as these interactions mediate a wide range of cellular processes. This study investigates the molecular interactions between TMA and acetate, representing carboxylate-containing groups, using neutron scattering experiments complemented by force field and ab initio molecular dynamics (MD) simulations. Neutron diffraction with isotopic substitution reveals specific ion pairing signatures between TMA and acetate, with simulations providing a detailed interpretation of the ion pairing structures. Force fields, notably CHARMM36 with the electronic continuum correction (ECC) (by a factor of 0.85) and AMBER99SB, capture essential pairing characteristics, but only revPBE-based ab initio MD simulations accurately model specific experimental features such as the low Q peak intensity in reciprocal space. Our study delivers a refined molecular model of TMA--carboxylate interactions, guiding the selection of force fields for complex biological systems where such interactions are of a significant importance.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"60 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874056","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 investigation of the photocatalytic properties of two-dimensional CdO/ZrSSe heterojunctions","authors":"Deming Ma, Xiaohan Hui, Xiaoyu Yang, Yuhui Fu, Zhen Cui, Lin Zhang, Weili Ji, Yang Shen, Enling Li","doi":"10.1039/d4cp03640a","DOIUrl":"https://doi.org/10.1039/d4cp03640a","url":null,"abstract":"Two-dimensional van der Waals heterojunction materials have demonstrated significant potential for photocatalytic water splitting in hydrogen production, owing to their distinct electronic and optical properties. Among these materials, direct Z-scheme heterojunctions have attracted considerable attention in recent research. In this study, a novel CdO/ZrSSe heterojunction is designed using first-principles calculations. The structural stability, electronic properties, carrier mobility, optical absorption, and photocatalytic performance of this heterojunction are systematically investigated, with a particular focus on the influence of strain on the band structure. The results reveal that both type-I and type-II heterojunctions exhibit staggered, indirect bandgap structures, with bandgap values of 0.80 eV and 0.60 eV, respectively. A built-in electric field is established from the CdO layer to the ZrSSe layer, facilitating oxidation in the ZrSSe layer and reduction in the CdO layer. The highest carrier mobilities are calculated to be 462 cm<small>²</small> V<small>⁻¹</small> s<small>⁻¹</small> and 2738 cm<small>²</small> V<small>⁻¹</small> s<small>⁻¹</small>, respectively. Under compressive strain, the bandgap widths of both I-CdO/ZrSSe and II-CdO/ZrSSe heterojunctions decrease, whereas tensile strain results in an increase in the bandgap width. Correspondingly, the optical absorption peaks of both heterojunctions are enhanced under compressive strain and diminished under tensile strain. These findings suggest that the performance of both type-I and type-II CdO/ZrSSe heterojunctions surpasses that of their individual monolayers, exhibiting a typical Z-scheme photocatalytic mechanism, and thus positioning them as promising high-efficiency catalysts for water splitting.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"114 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874057","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":"Chemical process of hydrogen and formic acid on a Pd-deposited Cu(111) surface studied by high-resolution X-ray photoelectron spectroscopy and density functional theory calculations","authors":"Wataru Osada, Masahiro Hasegawa, Yuichiro Shiozawa, Kozo Mukai, Shinya Yoshimoto, Shunsuke Tanaka, Mitsuaki Kawamura, Taisuke Ozaki, J. Yoshinobu","doi":"10.1039/d4cp03942d","DOIUrl":"https://doi.org/10.1039/d4cp03942d","url":null,"abstract":"Formic acid (HCOOH) is one of the essential molecules for CO<small>₂</small> utilization including methanol synthesis and hydrogen carriers. In this study, we have investigated the chemical processes of hydrogen and HCOOH on a dilute-alloy Pd-Cu(111) surface using high-resolution X-ray photoelectron spectroscopy (HR-XPS) and density functional theory (DFT) calculations. The present Pd-Cu(111) surface was prepared at 500 K, and the observed core-level shifts of Pd 3d<small>_5/2</small> indicate that Pd atoms were located at the surface and subsurface sites: 335.3 eV at the surface and 335.6 eV at subsurface sites, respectively. The coverage of surface Pd atoms was estimated to be 0.05 ML, indicating that the present Pd-Cu(111) surface acted as a single atom alloy catalyst. The C 1s and O 1s XPS spectra indicate that the surface chemistry of HCOOH on the present Pd-Cu(111) surface is almost equivalent to a bare Cu(111) surface; HCOOH is dissociated into monodentate formate and atomic hydrogen at 150-160 K, followed by conversion to bidentate formate species at 300 K, and finally it is decomposed and desorbed as CO<small>₂</small> + ½ H<small>₂</small> at ~450 K. The conversion ratio of adsorbed HCOOH to bidentate formate species on Pd-Cu(111) was 12 %, almost the same as that on Cu(111). That monodentate formate species and atomic hydrogen aggregate around the Pd atom is supported by the observed core-level shift of Pd 3d<small>_5/2</small> and systematic DFT calculations . The present DFT calculations also show that formate species are preferably adsorbed on the Cu site; thus, the Pd site is unoccupied by formate species at this stage. This implies that the present single atom alloy catalyst Pd-Cu(111) has an advantage during CO<small>₂</small> hydrogenation at lower temperature, where the Pd site can act as the H<small>₂</small> dissociation site without poisoning by formate intermediate species.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"140 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874061","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":"Dissipative particle dynamics parametrisation using infinite dilution activity coefficients: the impact of bonding","authors":"Rachel L. Hendrikse, Carlos Amador, Mark R. Wilson","doi":"10.1039/d4cp03791j","DOIUrl":"https://doi.org/10.1039/d4cp03791j","url":null,"abstract":"Dissipative particle dynamics (DPD) simulations have proven to be a valuable coarse-grained simulation technique for studying complex systems such as surfactant and polymer solutions. However, the best method to use in parametrising DPD systems is not universally agreed. One common approach is to map infinite dilution activity coefficients to the DPD simulation ‘beads’ that represent molecular fragments. However, we show that here that this approach can lead to serious errors when bonding beads together to create molecules. We show errors arise from the verlaps between bonded beads, which alters their solubility. In this article, we demonstrate how these bonding errors can be accounted for when defining DPD force fields using simple theoretical methods to account for the overlapping volumes, and we demonstrate the validity of our approach by calculating the partition coefficients for a series of solutes into two immiscible solvents.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"79 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874059","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":"Elucidate the mechanism behind the significant changes in photoluminescence behavior after powder compression into tablet","authors":"Xiao-Ping Lei, Qingfeng Wu, Xiangxi Zhang, Qing Zhou, Lingmin Yi","doi":"10.1039/d4cp03897e","DOIUrl":"https://doi.org/10.1039/d4cp03897e","url":null,"abstract":"Nonconventional luminogens have great potential applications in fields like anti-counterfeiting encryption. But so far, the photoluminescence quantum yield (PLQY) of most these powders is still relatively low and the persistent room temperature phosphorescence (p-RTP) emission is relatively weak. To improve their PLQY and p-RTP, pressing the powder into tablets has been preliminarily proven to be an effective method, but the specific mechanism has not been fully elucidated yet. Here, D-(+)-cellobiose has been chosen as the representative to solve the problem. The results showed that the PLQY and p-RTP lifetimes of the tablet of D-(+)-cellobiose were improved compared to the powder. By the mechanism of clustering-triggered emission (CTE) and theoretical calculations, it has been demonstrated that the enhanced molecular interactions after compression is the key reason, which resulting in the formation of cluster emission centers with stronger emission capabilities. And the combination of powder and tablet has been proven to be capable of advanced anti-counterfeiting encryption. The above results not only provide possible references for understanding the emission mechanism of small molecule and cellulose based emission materials, but also promote the process of more intuitive observation of emission centers for explaining emission mechanisms.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"32 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874031","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":"Negative Linear Compressibility of Molecular and Ionic-molecular Crystals","authors":"Dmitry Vasilevich Korabel'nikov, Igor Alexandrovich Fedorov","doi":"10.1039/d4cp03913k","DOIUrl":"https://doi.org/10.1039/d4cp03913k","url":null,"abstract":"The compressibility of crystalline tetrabromophthalic anhydride (TBPA) and 1-ethyl-3-methylimidazolium nitrate (EMN) was studied based on density functional theory including dispersion interactions at pressures below 1 GPa. It is found for the first time that EMN demonstrate negative linear compressibility (NLC) up to ~ 0.15 GPa, whereas TBPA shows significant NLC at pressures higher than ~ 0.2 GPa. Mechanisms of the observed negative linear compressibility of TBPA and EMN have been found at the microscopic (molecular) level for the first time. It was shown that NLC correlates with baric change of spatial orientation (rotation) and linear dimensions of molecular structural units relative to crystallographic axes, as well as with baric increase of intermolecular distances along NLC direction. Quantum topological analysis of electron density was used to study intermolecular interactions. It has been established that TBPA and EMN crystals are optically transparent for visible light at pressures up to 1 GPa.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"11 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874069","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}