Physical Chemistry Chemical Physics最新文献

{"title":"Atmospheric reactions of substituted butanes with OH radicals: kinetics and atmospheric implications.","authors":"Bishnupriya Kar, Balla Rajakumar","doi":"10.1039/d5cp00961h","DOIUrl":"10.1039/d5cp00961h","url":null,"abstract":"<p><p>2-Chlorobutane (2CB) and 2-aminobutane (2AB) are chiral compounds, which play a crucial role in biological complexity. These compounds can be released into the air through natural and man-made processes. Their emission into the atmosphere may influence the air quality and climate significantly. In the present work, the kinetics for the reactions of 2AB and 2CB were investigated experimentally and computationally at various temperatures. The rate coefficients for both reactions were evaluated using the SAR approach at 298 K. In addition, their impacts on the atmosphere have been discussed using atmospheric parameters. The experiments were performed using a pulsed laser photolysis - laser induced fluorescence technique for both reactions over 268-363 K. The rate coefficients were measured to be (2.42 ± 0.08) × 10^-12 and (3.03 ± 0.05) × 10^-11 cm³ molecule^-1 s^-1, for OH-initiated reactions of 2CB and 2AB, respectively. The computational calculations for these reactions were performed at the CCSD(T)/aug-cc-pVDZ//M06-2X/6-311+G(d,p) level of theory for 2CB and 2AB over 200-400 K. The rate coefficients were compared with changing the substituent on the butane chain. Cumulative atmospheric lifetime, radiative forcing, global warming potential, and acidification potential were calculated using the experimental and theoretical rate coefficients. In addition, the secondary organic compounds formed due to the reactions were analysed qualitatively using GC-MS and then compared with the theoretical results of the individual group contribution to the overall rate coefficients.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":"19852-19867"},"PeriodicalIF":2.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144936592","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":"Thermal conductivity of selenium crystals based on machine learning potentials.","authors":"Xiao Tang, Liangcai Wu, Ziang Xu, Lei Liu, Zhitang Song, Wenxiong Song","doi":"10.1039/d5cp02310f","DOIUrl":"10.1039/d5cp02310f","url":null,"abstract":"<p><p>Selenium, as an important semiconductor material, exhibits significant potential for understanding lattice dynamics and thermoelectric applications through its thermal transport properties. Conventional empirical potentials are often unable to accurately describe the phonon transport properties of selenium crystals, which limits in-depth understanding of their thermal conduction mechanisms. To address this issue, this study developed a high-precision machine learning potential (MLP), with training datasets generated <i>via ab initio</i> molecular dynamics simulations. Validation demonstrated that the phonon dispersion relations calculated by the MLP showed excellent agreement with density functional theory results. Using this potential, we systematically investigated the thermal transport properties of trigonal (t-Se) and monoclinic selenium (m-Se). The results demonstrate that t-Se exhibits higher thermal conductivity. Phonon density of states analysis reveals that this originates from its chain-like structure (where intrachain atoms are connected by strong covalent bonds while interchain interactions occur through weaker van der Waals forces), which enables stronger thermal transport compared to the ring-like structure of m-Se. The electronic structure calculations further reveal that the bandgap of t-Se is significantly smaller than that of m-Se (by approximately 0.7 eV). Therefore, although t-Se exhibits a relatively large lattice thermal conductivity, its higher electrical conductivity (<i>σ</i>) (six orders of magnitude difference) and Seebeck coefficient compensate for this disadvantage, enabling t-Se to achieve a high <i>ZT</i> (<i>σ</i>/<i>κ</i> ratio) and superior thermoelectric potential.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":"20334-20343"},"PeriodicalIF":2.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028601","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":"Core-level binding energies describe electrostatic potentials at nuclei for ionic liquids","authors":"Frances Towers Tompkins, Ekaterina Gousseva, Roger Bennett, Ricardo Grau-Crespo, Kevin R. J. Lovelock","doi":"10.1039/d5cp02411k","DOIUrl":"https://doi.org/10.1039/d5cp02411k","url":null,"abstract":"Electrostatic interactions in ionic liquids (ILs) dictate many of their physical properties and hence underpin a plethora of potential applications. It is vital to develop both experimental and theoretical electronic descriptors for ILs, to drive deeper understanding of the interactions that may be tuned for applications. A possible descriptor for ILs is the readily measurable core-level binding energy from experimental core-level X-ray photoelectron spectroscopy (XPS), <em>E</em><small>_B</small>(core). To establish that differences in <em>E</em><small>_B</small>(core) capture the differences in electrostatic potential at nuclei, <em>V</em><small>_n</small>, we use a computational approach based on ab initio molecular dynamics (AIMD). We demonstrate clear quantitative (linear) correlations between experimental <em>E</em><small>_B</small>(core) and calculated <em>V</em><small>_n</small> for carbon, nitrogen, sulfur, oxygen and fluorine for both cations and anions. Our work shows that <em>E</em><small>_B</small>(core) are interpretable descriptors of electrostatic interactions in ILs. This has implications for the ability to predict, out of the vast number of ILs that can form from the array of available cations and anions, the best IL properties for target applications. We also discuss how this work could open up new areas of enquiry, including about the usefulness of <em>V</em><small>_n</small> to characterise interactions of ILs with surfaces and interfaces.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"40 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127919","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":"Mechanistic insights into electric field-dependent polarization and kinetics of the elementary reaction NH + H2 → NH2 + H.","authors":"Jie Chen,Jia Ma,Nan Liu,Qi Chen,Lidong Zhang","doi":"10.1039/d5cp03412d","DOIUrl":"https://doi.org/10.1039/d5cp03412d","url":null,"abstract":"The elementary reaction NH + H2→ NH2 + H is a pivotal pathway in the NH3 reaction network, yet its polarization mechanism and kinetic parameters under external electric fields (EEFs) remain unexplored despite well-established equilibrium kinetics. Here, we employ CCSD(T)/CBS//M06-2X/6-311G(d,p) calculations and transition state theory to systematically investigate 23 EEF directions across 0.005-0.03 a.u., revealing cooperative control of reaction kinetics by the field direction and strength. Alignment with the reaction axis (e.g., -X, (-X, Y), and (-X, Y, -Z)) enhances rate constants by 4 orders of magnitude at 0.03 a.u., while misaligned planar fields suppress reactivity at 0.02 a.u. Crucially, field orientation governs product selectivity through charge transfer that exhibits exponential sensitivity to field strength. The molecular rearrangement induced by the EEFs ensures that the reaction proceeds along the most favorable path. As a result, three advantageous directions, (-X), (-X, Y), and (-X, Y, -Z), were selected for further analysis. By calculating the electronic structure and employing molecular orbital theory, valence bond theory and the quantum theory of atoms in molecules (QTAIM) method, it was found that the reaction responds to EEFs due to the initial regulation of molecular polarity and the influence of the electric field on the charge transfer during the reaction. The results also show that the dipole moment of the transition state is significantly reduced by EEFs in different (-X, Y, and -Z) directions, initially decreasing and then increasing with increasing field strength. The electrostatic potential distribution further illustrates the regulatory effect of different electric field directions on reaction products. Additionally, the EEFs along the reaction axis direction significantly lower the LUMO energy level of the transition state, which may reduce the probability of ionic/charge transfer state wavefunctions mixing into the transition state wavefunction. These findings establish a quantitative framework for leveraging EEFs to manipulate energy barriers and orbital interactions, offering mechanistic insights for optimizing product yields in EEF-driven ammonia reaction systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"84 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127404","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":"Nucleophilicity of diatomic Lewis bases MA in Hydrogen-bonded Complexes MA⋯HX: Influence of Group and Row of M in the Periodic Table. 1","authors":"Ibon Alkorta, Anthony C Legon","doi":"10.1039/d5cp03257a","DOIUrl":"https://doi.org/10.1039/d5cp03257a","url":null,"abstract":"Nucleophilicities N MA of diatomic Lewis bases MA acting as hydrogen-bond acceptors in complexes MA⋯HX are reported. The molecules MA were chosen so that the atom M adjacent to the atoms A directly involved in the hydrogen bonds belonged to Groups 13, 14, 15, 16 and 17 of the Periodic Table. The effects of changing atom M from Rows 1 to 4 within a given Group were also investigated. The hydrogen-bond donors HX involved in the complexes were HF, HCl, HBr, HI, HCCH, and HCP. Nucleophilicities N MA were determined from dissociation energies D e for the process MA⋯HX = MA + HX by using D e = cN MA .E HX + d, where E HX are electrophilicities of the Lewis acids HX, and c and d are constants. The order of NM A values was found to be: Row 4 &gt; Row3~ Row2 &gt;&gt; Row 1 in each of the Groups 13, 15, 15, 16 and 17. The effect of adding an H atom to MA to give linear triatomic molecules HMA is considered. The reduced nucleophilicities И MA = N MA /σ min (σ min is the minimum value of the molecular electrostatic surface potential of MA) as a function of Group and Row of atom M were also discussed for diatomic molecules MA. 1 Dedicated to Professor Resnati, celebrating a career in fluorine and noncovalent chemistry on the occasion of his 70 th birthday.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"40 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116479","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":"Enhanced photocatalytic degradation and CO2 reduction activity of S-type ZnCdS/BiOBr heterojunction composites: mechanism insights and pathway analysis","authors":"Chenyang Sun, Yongkuan Zhang, Lijing Di, Tao Xian, Xiaofeng Sun, Hua Yang","doi":"10.1039/d5cp02890f","DOIUrl":"https://doi.org/10.1039/d5cp02890f","url":null,"abstract":"S-type ZnCdS/BiOBr heterojunction photocatalysts were successfully created by the attachment of ZnCdS nanoparticles on the surface of BiOBr nanosheets. Upon simulated sunlight irradiation, the photocatalytic activity of ZnCdS/BiOBr composites for the removal of dyes (methyl orange (MO) and methylene blue (MB)) and an antibiotic (tetracycline (TC)) was systematically investigated. The findings suggested that the photodegradation performance of BiOBr was apparently improved after decoration with ZnCdS nanoparticles. The 4% ZnCdS/BiOBr sample manifested an optimal photocatalytic degradation activity, and compared with bare BiOBr, its removal rates for MB, MO and TC were improved by ∼2.8, ∼4.6 and ∼2.9 times, respectively. The probable degradation pathway of TC was studied in detail. On the other hand, the photocatalytic CO<small>₂</small> reduction activity of the products was concurrently tested <em>via</em> excitation by simulated sunlight. The ZnCdS/BiOBr composites exhibited an enhanced catalytic performance for the reduction of CO<small>₂</small> into CO compared with BiOBr. Among them, the 4% ZnCdS/BiOBr sample had the best CO yield rate of 2.61 μmol g<small>⁻¹</small> h<small>⁻¹</small> (4 h reaction), which is ∼1.68 times higher than that of bare BiOBr. The possible photocatalytic CO<small>₂</small> reduction pathway was also predicted. The potential photocatalytic mechanism of the S-type ZnCdS/BiOBr heterojunction was proposed.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"39 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116480","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":"Quantum mechanics insights into the early pyrolysis mechanism of 3,4-dinitro-1H-pyrazole in the amorphous model","authors":"Shuang-Fei Zhu, Shufen Zheng, Wen-jun Rao, Yi Yang, Rui-Jun Gou, Shu-hai Zhang","doi":"10.1039/d5cp03087k","DOIUrl":"https://doi.org/10.1039/d5cp03087k","url":null,"abstract":"Self-consistent charge density-functional tight binding molecular dynamics simulations reveal distinct thermal decomposition pathways between crystalline and amorphous 3,4-dinitro-1H-pyrazole (DNP). Key findings include prolonged equilibrium in amorphous systems and dominant NO₂/H dissociation mechanisms. Results show that the potential energy evolution of the crystalline model is similar to that of the amorphous model, in which the amorphous model shows a longer equilibrium stage. Four important decomposition reactions were identified, including NO2 dissociation, H dissociation, H attacking the nitro group, and N-N bond cleavage. The former two reactions are dominant in the decomposition of DNP, and the dissociation of 1-position hydrogen and 3-position nitro group is easier, which is also supported by quantum chemical calculations. For the ring-opening reaction, there is small difference between the two models, primarily involving the N-N bond breakage and C-N bond cleavage to form N2. In addition, more hydrogen dissociation reactions occur in the crystalline model, therefore, DNP in the crystalline model is more likely to decompose, and the products are generated earlier than the amorphous model. These results contribute to our understanding of thermal decomposition of energetic materials with layered structure.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"317 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116481","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":"Finding heterogeneous nucleating agents for ice using a data-driven approach","authors":"Zixuan Wang, David E. Oliver, Andrew J. Bissell, Gylen Odling, Colin R. Pulham, Carole A. Morrison","doi":"10.1039/d5cp02701b","DOIUrl":"https://doi.org/10.1039/d5cp02701b","url":null,"abstract":"We present a high-throughput data-driven workflow to identify potential heterogeneous nucleating agents from structural databases for phase change materials, such as ice. Our model evaluates the fit between ice-Ih and nucleator docked slabs, considering Miller index planes up to (3,3,3), thus addressing some of the structural complexities in nucleation by examining crystal morphology features. Bulk water immersion experiments on a set of ten known nucleators set a delineating temperature to distinguish between good and poor nucleation behaviour, which helped derive numerical tolerance limits to allow reliable differentiation on the basis of the number of predicted matching interface models. We then used our algorithm to screen 3,500 simple metal oxides and halides taken from the Inorganic Chemistry Structural Database (ICSD), and show that just 7% of the former and 3% of the latter were predicted to nucleate ice on the basis of geometric slab matching. Subsequent experimental testing of 22 compounds suggested a 64% correct prediction rate, and identified four new ice nucleators (CeO2, WO3, Bi2O3, Ti2O3). Inspired by the ice-nucleating efficiency of copper oxides, we also tested copper tubing with local tap water, and observed sub-cooling suppression, most likely due to copper oxide buildup. Although based on a simple geometric interface matching model, this approach offers an efficient route to screen for heterogeneous nucleating agents.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"90 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116508","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":"The Role of Electronic Structure in the Hydrogen Evolution Reaction Dynamics as Catalyzed by Ru-based Complexes","authors":"Andrea Severini, Camilla Ferrari, Marianna Burello, Francesco Vizza, Marco Bonechi, Riccardo Chelli, Massimo Innocenti, Fabrizio Roncaglia, Claudio Fontanesi","doi":"10.1039/d5cp03035h","DOIUrl":"https://doi.org/10.1039/d5cp03035h","url":null,"abstract":"The catalytic activity for the hydrogen evolution reaction of three structurally related ruthenium catalysts is compared: a di-nuclear [Ru 2 (OTf)(m-H)(Me 2 dad)(dbcot) 2 ] (C1) and two mononuclear analogues (C2, C3). The reaction mechanism is analyzed at a molecular level by using ab-initio DFT calculation to determine singular-points on the potential energy surface (PES). Then, time dependent behavior is investigated by calculationing molecular dynamic (MD) trajectories, within the Dynamic Reaction Coordinate (DRC) paradigm. Displacement of molecular hydrogen results the ratedetermining step. C2 shows a promising low activation barrier: 8.6 kcal/mol, although H 2 release is kinetically slower. C3 yields molecular hydrogen but fails its release, even when provided with kinetic energy larger than the activation barrier (24.4 kcal/mol), revealing unforeseen mechanistic traps, beyond purely energetic considerations. This work underscores how ligand coordination flexibility critically affects the efficiency of hydrogen catalysis, paving the way for the rational design of novel catalysts.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"162 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116507","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":"Theoretical and kinetic study of H-abstraction from diisopropyl ether by key radicals: implications for combustion chemistry","authors":"xingzhi Wang, Jiuning He, xue Zou, Jianhua Li, lei chen, yanhao Duan, Jia Li, Changhua Zhang, De-Liang Chen","doi":"10.1039/d5cp02388b","DOIUrl":"https://doi.org/10.1039/d5cp02388b","url":null,"abstract":"H-abstraction by reactive radicals OH, HO2, H, and CH3 governs diisopropyl ether (DIPE) oxidation kinetics, with preferential attack at α-carbon sites adjacent to the ether oxygen. Current kinetic models exhibit significant uncertainties due to scarcity of high-level experimental and theoretical data, necessitating rate estimation via structural analogs. To resolve these gaps, we employed high-accuracy multi-structural variational transition state theory with small-curvature tunneling correction (MS-VTST/SCT) coupled with M06-2X/cc-pVTZ//M08-HX/def2-tzvp (M08-HX/def2-tzvp is the combination with the smallest MUD value based on DLPNO-CCSD(T)/CBS(T-Q)) calculations. This approach systematically investigates H-abstraction across all carbon sites in DIPE + OH/HO2/H/CH3 systems. Activation energies of –0.62 to 22.69 kcal·mol⁻¹ reveal hydrogen-bonded complexes RCαOH and RCβ1HO2 stabilizing transition states in OH/HO2 pathways. Detailed analysis of temperature-dependent rate constants (200–1700 K) and branching ratios uncovers dominant torsional/anharmonic effects on microcanonical pathways: In DIPE + OH, R1a dominates below 550 K owing to hydrogen-bond-induced barrier reduction while R1b prevails at higher temperatures due to enthalpy advantage; R3a and R4a consistently control DIPE + H/CH3 consumption across combustion-relevant conditions. The total rate for DIPE + OH, ktotal=0.1015×T4.514exp(-3457.125/T) cm³·mol⁻¹·s⁻¹, not only agrees excellently with experimental data but also reveals non-Arrhenius behavior above 450 K. Implementation of these first-principles rates in an updated combustion model substantially improves predictions of CH3COCH3. C3H6 and C2H6 species profiles in jet-stirred reactor experiments at φ=1.0, 1 atm. Reaction pathway analysis further quantifies H-abstraction as the primary DIPE consumption route, contributing &gt;75% fuel depletion below 900 K.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"79 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116512","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}