Physical Chemistry Chemical Physics最新文献_第10页

Questioning the Role of Adsorbed H in H₂O₂ Decomposition on Pt(111) for the Electrocatalytic Green Fenton Process 电催化绿芬顿法Pt（111）上H₂O₂分解中吸附H的作用

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-09-23 DOI: 10.1039/d5cp03100a

Chentao Xu, Ji Li, Zhizhang Shen

{"title":"Questioning the Role of Adsorbed H in H₂O₂ Decomposition on Pt(111) for the Electrocatalytic Green Fenton Process","authors":"Chentao Xu, Ji Li, Zhizhang Shen","doi":"10.1039/d5cp03100a","DOIUrl":"https://doi.org/10.1039/d5cp03100a","url":null,"abstract":"To overcome the limitations of traditional Fenton processes (such as narrow operating pH range and iron precipitation), an electrocatalytic green Fenton process mediated by adsorbed hydrogen (H*) was proposed. However, the role of H* in H 2 O 2 decomposition remains debated, and the solvent effects have been overlooked in previous studies. To address these gaps, we employed density functional theory (DFT) calculations combined with the blue moon ensemble (BME) method to examine how H* and H 2 O alter the free energy profiles of H 2 O 2 decomposition into hydroxyl radicals ( • OH) on Pt(111). Free energy analysis demonstrates that H 2 O 2 decomposition is exothermic in systems containing either H* or surface water, with the latter scenario being more favorable. In contrast, H* kinetically hinders the decomposition by raising the activation barrier to 0.356 eV (vs. 0.165 eV on pristine Pt( 111)), whereas the process becomes almost barrierless (0.029 eV) when water molecules are present. DFT based molecular dynamics simulations further demonstrate that in systems with coadsorbed H* and H 2 O, the water-mediated H 2 O 2 decomposition pathway dominates. Our results challenge the current understanding of H 2 O 2 decomposition pathways, revealing the critical mechanistic role of surface water and offering new insights for optimizing electrocatalytic Fenton processes.","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":"145116510","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

High-throughput DFT screening of bimetallic alloys for selective ammonia synthesis via electrocatalytic N2 activation. 电催化N2活化双金属合金的高通量DFT筛选。

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-09-23 DOI: 10.1039/d5cp02242h

Zhaoyu Qi,Shun Li,Shitao Peng

{"title":"High-throughput DFT screening of bimetallic alloys for selective ammonia synthesis via electrocatalytic N2 activation.","authors":"Zhaoyu Qi,Shun Li,Shitao Peng","doi":"10.1039/d5cp02242h","DOIUrl":"https://doi.org/10.1039/d5cp02242h","url":null,"abstract":"Ammonia, a cornerstone of modern agriculture and a promising carbon-free energy carrier, is conventionally synthesized via the energy-intensive Haber-Bosch process. In pursuit of sustainable alternatives, electrocatalytic nitrogen reduction reaction (NRR) has garnered significant attention. However, the inert NN triple bond and the competing hydrogen evolution reaction (HER) pose formidable challenges. This study pioneers an integrated computational approach, combining high-throughput density functional theory (DFT), machine learning, and ab initio thermodynamics, to identify and rationalize high-performance bimetallic NRR catalysts. Among 20 screened alloys, CoRu emerges as a Pareto-optimal catalyst, demonstrating exceptional activity, selectivity, and stability. Ru's unique electronic modulation, manifested through orbital-selective hybridization and interfacial dipole fields, decouples the traditional trade-offs between NRR activity and HER suppression. Mechanistic insights reveal that CoRu facilitates moderate N2 adsorption and a record-low overpotential of 0.28 V, while suppressing HER to achieve a faradaic efficiency of 72%. Furthermore, machine learning models trained on DFT-derived descriptors enable inverse design of novel alloys, predicting NiRu as a high-potential candidate. This study not only decodes the electronic origins of bimetallic synergy but also provides a blueprint for accelerating the discovery of next-generation electrocatalysts, heralding a transformative strategy to replace energy-intensive Haber-Bosch processes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"11 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145117104","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

Highly anisotropic electronic properties of the GdBa2Ca2Fe5O13 oxide: a DFT+U study of a potential air electrode for solid oxide fuel cells GdBa2Ca2Fe5O13氧化物的高各向异性电子特性：固体氧化物燃料电池潜在空气电极的DFT+U研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-09-23 DOI: 10.1039/d5cp01780g

Boris Politov, Susana García-Martín, Igor R. Shein

{"title":"Highly anisotropic electronic properties of the GdBa2Ca2Fe5O13 oxide: a DFT+U study of a potential air electrode for solid oxide fuel cells","authors":"Boris Politov, Susana García-Martín, Igor R. Shein","doi":"10.1039/d5cp01780g","DOIUrl":"https://doi.org/10.1039/d5cp01780g","url":null,"abstract":"Profound knowledge of the electronic structure of functional solids is essential to understand and optimize their properties. The current advances in electronic structure theory, together with the improvements in computing power, permit to realize affordable calculations of electronic structure of complex solids with the aim of explaining or predicting properties of singular materials. This work presents a Density Functional Theory study of the GdBa2Ca2Fe5O13 oxide,a potential air electrode for solid oxide fuel cells with layered-perovskite-related structure, which presents ordering of three different coordination-polyhedron around the Fe3+ ions (FeO6 octahedra, FeO5 squared pyramids and FeO4 tetrahedra). The existence of these three different Fe-environments highly impact on the electronic properties of this oxide. The band structure of the GdBa2Ca2Fe5O13 concludes that the FeO5 layers create the CB (conduction band), the FeO6-layers form the VB (valence band) and the FeO4 layers create insulating channels, leading to anisotropic electrical properties that coincide with the experimentally observed 2D magnetic, electrical, and structural characteristics of the GdBa2Ca2Fe5O13.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"8 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116478","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

Are supramolecular synthons stable as discrete units? Results from a series of salts of 4-(4-hydroxyphenylazo)benzoic acid and its derivatives with aminopyridines 超分子合成物作为离散单位稳定吗？4-（4-羟基苯基偶氮）苯甲酸及其氨基吡啶衍生物系列盐的研究结果

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-09-23 DOI: 10.1039/d5cp03325j

Munendra Pal Singh, Abhinav Hazarika, Jubaraj B. Baruah

{"title":"Are supramolecular synthons stable as discrete units? Results from a series of salts of 4-(4-hydroxyphenylazo)benzoic acid and its derivatives with aminopyridines","authors":"Munendra Pal Singh, Abhinav Hazarika, Jubaraj B. Baruah","doi":"10.1039/d5cp03325j","DOIUrl":"https://doi.org/10.1039/d5cp03325j","url":null,"abstract":"Analysis of a supramolecular synthon is an integral part of understanding, describing, and designing non-covalent assembly. The energies of synthons play a key role in the formation and disruption to result in the conversion to a new assembly. It also provides scopes to understand their collective effects by being a part of an assembly. We have performed a structural study and analyzed the synthons in 4-(4-hydroxyphenylazo)benzoic acid (H2AZOBEN) and its salts with 2-aminopyridine, 4-aminopyridine, and pyrimidin-2-amine derivatives to show the collective contributions to stability from synthons. The energies of identified synthons from observed crystal structures were independently optimized by DFT calculation with M062X density functional together with the QZVP and 6-311+G(d,p) basis set. MM2-surface charge-density calculation on the salt of formic acid with aminopyridine or aminopyrimidine established that the geometrical arrangements in discrete combinations are not through the complementary hydrogen-bonded heterodimers, but the anion and cation have perpendicular orientations. The crystal structure of the hydrate of H2AZOBEN showed the presence of a hydrogen-bonded water bridge, and theory has suggested that this was the key feature in the stabilization of the assembly. Similarly, the gain in energy by hydration in hydrates was compared with the energy of different synthons in anhydrous forms, to show that hydration is the key to the stability of those. The combined effects of different synthons were found as a factor in providing relative stability compared to a single one. In the assemblies of methoxy or ethoxy derived H2AZOBEN, the ethereal oxygen did not participate in the scheme of hydrogen bonds. This is attributed to the C-H…π interactions of the C-H bond of the methyl and ethyl groups provide directional property to the assembly and also provide an environment to the O-atom without a good hydrogen bond acceptor in its proximity.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"9 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116509","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}

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Hydrogen bonding and van der Waals forces contributions to the melting enthalpy: insights from volumetric and spectroscopic data 氢键和范德华力对熔化焓的贡献：来自体积和光谱数据的见解

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-09-22 DOI: 10.1039/d5cp02393a

Andrey A. Sokolov, Boris N. Solomonov, Mikhail I. Yagofarov

{"title":"Hydrogen bonding and van der Waals forces contributions to the melting enthalpy: insights from volumetric and spectroscopic data","authors":"Andrey A. Sokolov, Boris N. Solomonov, Mikhail I. Yagofarov","doi":"10.1039/d5cp02393a","DOIUrl":"https://doi.org/10.1039/d5cp02393a","url":null,"abstract":"The investigation of the hydrogen bonding influence on the thermodynamic properties of matter is of great importance for both fundamental and applied science. In this work, we analyzed the relationship between the fusion enthalpies and volume changes on melting for associated molecular substances. The relationship between the enthalpy-to-volume ratio and the molecular sphericity parameter previously found for non-hydrogen-bonded systems enabled the division of the fusion enthalpy into van der Waals and specific interactions contributions. On the other hand, hydrogen bonding strength change on melting was evaluated based on the Badger-Bauer rule. These two independent estimates of the hydrogen bonding effect on the fusion enthalpies agreed within 1.1 kJ mol-1 on average for a diverse set of alcohols, phenols, carboxylic acids, and water. Thus, an approach for studying a complicated balance between hydrogen bonding and van der Waals forces contributions into the fusion enthalpy of non-electrolytes, combining the spectroscopic, calorimetric, and volumetric data, accounting for their molecular structure, was developed for the first time.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"39 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145116511","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

Assessing the accuracy of DFT functionals and ab initio methods for the description of multireference verdazyl radical crystalline interactions 评估DFT泛函和从头算方法描述多参比verdazyl自由基晶体相互作用的准确性

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-09-22 DOI: 10.1039/d5cp02287h

James Ross Brookes, Peter Daniel Watson, Duncan A Wild, Stephen A. Moggach, Dino Spagnoli

{"title":"Assessing the accuracy of DFT functionals and ab initio methods for the description of multireference verdazyl radical crystalline interactions","authors":"James Ross Brookes, Peter Daniel Watson, Duncan A Wild, Stephen A. Moggach, Dino Spagnoli","doi":"10.1039/d5cp02287h","DOIUrl":"https://doi.org/10.1039/d5cp02287h","url":null,"abstract":"Verdazyl radicals represent a class of organic compounds that are viewed as candidates for new electronic and magnetic materials. The performance of a range of density functional theory and wavefunction theory (ab initio) methods for the calculation of interaction energies of verdazyl radical dimers is evaluated. Reference energies are NEVPT2(14,8) interaction energies, with an active space comprised of the verdazyl π orbitals. Members of the Minnesota functional family are the top performing functionals for this purpose, namely the range-separated hybrid meta-GGA functional M11 and MN12-L, as well as the hybrid meta-GGA M06 and meta-GGA M06-L. The performance for these methods compared to a smaller 2 orbital, 2 electron basis set was also explored. Effects of restricted open-shell HF, dispersion corrections and the calculation of singlet-triplet gaps was also investigated. Methods for the high throughput determination of interaction energies in verdazyl radical crystals are presented. This work aids in the development of new molecular solid based electronic components, by enabling energy frameworks of verdazyl radical systems to be calculated accurately and confidently with lower computational costs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"52 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103706","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

Kinematic and thermodynamic studies on water micro-droplets supercooled in a vacuum 微水滴在真空中过冷的运动学和热力学研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-09-22 DOI: 10.1039/d5cp02281a

Takefumi Handa, Masashi Arakawa, Masato Yamaguchi, Takuya Horio, Akira Terasaki

{"title":"Kinematic and thermodynamic studies on water micro-droplets supercooled in a vacuum","authors":"Takefumi Handa, Masashi Arakawa, Masato Yamaguchi, Takuya Horio, Akira Terasaki","doi":"10.1039/d5cp02281a","DOIUrl":"https://doi.org/10.1039/d5cp02281a","url":null,"abstract":"Evaporation of water droplets in a vacuum induces rapid evaporative cooling that leads to a supercooled state of water. Observation of supercooled water provides valuable insights into ice nucleation and subsequent freezing processes. Here we introduce 40-μm water droplets into a vacuum to study their cooling and freezing dynamics by several experimental techniques. High-speed imaging is employed to observe oscillatory distortion that reflects surface tension and viscosity of the supercooled droplets and to capture fragmentation of freezing droplets. Observation of whispering gallery modes in the OH stretching Raman band enables precise measurement of the droplet size in the course of evaporation. Furthermore, a freezing curve, i.e., a fraction of frozen droplets as a function of time, is measured by capturing laser-scattering images to discriminate between frozen and unfrozen droplets. The experimental approaches to the evaporation rate and subsequent freezing time, along with thermodynamics simulation based on the Knudsen theory, allow us to discuss homogeneous ice nucleation rates between 232 and 235 K.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"7 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103705","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

Superconductivity Induced by Element Doping in C 48 Fullerene at Ambient Pressure 常温下c48富勒烯中元素掺杂诱导的超导性

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-09-22 DOI: 10.1039/d5cp03360h

Weiguo Sun, Dexin Mu, Xiaofeng Li, Simin Li, Feng Peng

{"title":"Superconductivity Induced by Element Doping in C 48 Fullerene at Ambient Pressure","authors":"Weiguo Sun, Dexin Mu, Xiaofeng Li, Simin Li, Feng Peng","doi":"10.1039/d5cp03360h","DOIUrl":"https://doi.org/10.1039/d5cp03360h","url":null,"abstract":"To investigate the superconducting potential of cage-type carbon compounds under ambient pressure, a pristine all-carbon C 48 fullerene structure is designed and doped with various elements. By optimizing the occupancy of group IA, IIA, and IIIA elements at dierent sites within the C 48 framework, we have obtained both stable metallic M 2 C 24 (M = Li, Na, Mg, Al, Ga, In) and H 2 C 24 structures. First-principles calculations results demonstrate that metal atoms, serving as electron donors, can induce a semiconductor-to-metal transition in the C 24 clathrate, while preserving high structural rigidity with a Vickers hardness exceeding 25 GPa. Further analysis of the superconducting properties reveals that the enhanced electronic state density at the Fermi level, driven by the vibration of the rigid carbon framework and elemental doping, enables Li 2 C 24 to exhibit a superconducting transition temperature (T c ) of 12.71 K at ambient pressure. Similarly, the doping of non-metallic hydrogen eectively tunes HC 24 into a superconductor with a T c of 8.39 K. This study deepens the understanding of superconductivity in carbon cage compounds and opens new avenues for realizing high-temperature superconductors through hole doping and other modulation strategies.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"16 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103758","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

Two-dimensional Janus 1T-ScTeX (X = Cl, Br, I) monolayers for high-efficiency energy conversion applications. 二维Janus 1T-ScTeX （X = Cl, Br， I）单层，用于高效能量转换应用。

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-09-22 DOI: 10.1039/d5cp03103f

Xiao-Long Jiang,Guo-Xiang Zhou,Tong-Tong Yan,Xu-Chen Qin,Jia Li

{"title":"Two-dimensional Janus 1T-ScTeX (X = Cl, Br, I) monolayers for high-efficiency energy conversion applications.","authors":"Xiao-Long Jiang,Guo-Xiang Zhou,Tong-Tong Yan,Xu-Chen Qin,Jia Li","doi":"10.1039/d5cp03103f","DOIUrl":"https://doi.org/10.1039/d5cp03103f","url":null,"abstract":"In this paper, the properties of Janus 1T-ScTeX (X = Cl, Br, I) monolayers have been thoroughly examined based on first-principles calculations. The results confirm that these materials are stable and highly flexible. Each monolayer exhibits an indirect bandgap semiconductor nature and its bandgap values and edge positions can be effectively controlled by biaxial strain. Janus 1T-ScTeX monolayers exhibit significant out-of-plane piezoelectricity, with 1T-ScTeCl showing the highest out-of-plane piezoelectricity coefficient (3.90 pm V-1) and notable strain sensitivity. 1T-ScTeBr has an electron mobility of up to 8844.50 cm2 V-1 s-1 in the y-direction. The materials display a wide range of high-efficiency light absorption characteristics on the order of 105 cm-1 in the infrared to ultraviolet region. The combination of suitable band edge positions, outstanding out-of-plane piezoelectric effects, high carrier mobility, and efficient light absorption gives 1T-ScTeX monolayers excellent potential for photocatalytic water splitting. Among them, 1T-ScTeI becomes the optimal candidate material due to its ability to simultaneously meet the redox potential requirements for water splitting over a wide pH range. Given these properties, Janus 1T-ScTeX monolayers show promising applications in flexible electronics, piezoelectric transducers, and photocatalysis.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"38 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103352","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

Two-Dimensional Ring Polymer Molecular Dynamics Determination of the MnO + + H 2 /D 2 Reaction Rates on a Δ-Machine Learned Potential Energy Surface 二维环形聚合物分子动力学：Δ-Machine学习势能表面上mno++ h2 / d2反应速率的测定

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-09-22 DOI: 10.1039/d5cp03026a

Yang Liu, Chen Li, Milan Ončák, Hua Guo

{"title":"Two-Dimensional Ring Polymer Molecular Dynamics Determination of the MnO + + H 2 /D 2 Reaction Rates on a Δ-Machine Learned Potential Energy Surface","authors":"Yang Liu, Chen Li, Milan Ončák, Hua Guo","doi":"10.1039/d5cp03026a","DOIUrl":"https://doi.org/10.1039/d5cp03026a","url":null,"abstract":"In this work, we investigate the impact of nuclear quantum effects in the kinetics of the MnO + + H 2 reaction, a prototypical system for gas-phase H 2 activation by transition metal oxide ions. The DFT based potential energy surfaces (PESs) for the lowest-lying quintet and septet spin states reported in our previous work [J. Phys. Chem. A, 2025, 129, 6306-6314] are improved by 2,953 newly calculated CCSD(T)/AVDZ points using a delta-machine learning (Δ-ML) method. To examine nuclear quantum effects, the rate coefficients are computed using ring-polymer molecular dynamics (RPMD). Due to mechanistic complexity of the reaction, two reaction coordinates are necessary to map out the free-energy surface and an extended RPMD rate theory is developed. The calculated RPMD rate coefficients on the new PES are in better agreement with experimental data.The calculated kinetic isotope effects (KIEs) range from 1.6 to 1.8, also in good agreement with the experimental values. In addition, the converged RPMD rate coefficients are 2.3 to 3.1 times higher than their classical counterparts across the studied temperature range, suggesting the presence of moderate nuclear quantum effects in this reaction.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"60 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103755","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