Physical Chemistry Chemical Physics最新文献_第3页

Evaluation of ultrananocrystalline diamond size by UV Raman spectroscopy and phonon confinement model 用紫外拉曼光谱和声子约束模型评价超晶金刚石的尺寸

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp02967h

Niranjan Kumar, Kalpataru Panda, Alexey Titovich Kozakov, Anatolay Nikolskii, V. A. Volodin, Sergey V. Goryainov

引用次数: 0

Fixed node-diffusion Monte Carlo achieves chemical accuracy in predicting substituent effects on activation energies and reaction enthalpies for methyl radical addition to substituted olefins 固定节点扩散蒙特卡罗在预测取代基对甲基自由基加成取代烯烃的活化能和反应焓的影响方面达到了化学精度

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp02300a

Timothy B. Huber, Ralph A. Wheeler

{"title":"Fixed node-diffusion Monte Carlo achieves chemical accuracy in predicting substituent effects on activation energies and reaction enthalpies for methyl radical addition to substituted olefins","authors":"Timothy B. Huber, Ralph A. Wheeler","doi":"10.1039/d5cp02300a","DOIUrl":"https://doi.org/10.1039/d5cp02300a","url":null,"abstract":"Computing accurate activation barriers and reaction enthalpies is essential for the development of kinetic mechanisms and prediction of reaction outcomes. However, the computationally intensive nature of accurate quantum calculations and lack of experimental data present challenges. In this study, eighteen radical addition reactions relevant to free radical polymerization were used to assess the accuracy of single reference fixed-node diffusion Monte Carlo (FN-DMC) in predicting activation barriers and reaction enthalpies. Using CCSD(T)/aug-cc-pVTZ as a reference, FN-DMC acquired a mean absolute deviation (MAD) of 4.5(5) kJ/mol for activation energies and 3.3(5) kJ/mol for reaction enthalpies. Activation energies and reaction enthalpies relative to the unsubstituted olefin exhibited relative MAD values of 1 kJ/mol and accurately predicted trends in substituent effects within statistical margins, except for activation energies of the methoxy and methylbutanenitrile analogs. With the demonstrated accuracy, favorable computational scaling, and highly parallelizable nature of FN-DMC, it should now be feasible to use FN-DMC to investigate activation energies and reaction enthalpies for larger systems, such as oligomers, where coupled-cluster-based methods may be limited by computational resources.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"21 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209861","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

Electronic charge density distortions due to dispersion: Physically meaningful DMA multipoles for H2, HeH, and He···He 色散导致的电子电荷密度扭曲：H2、HeH和He···He的物理意义上的DMA多极子

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp01955a

Nathan Jansen, Hua-Kuang Lee, Katharine Clarke Hunt

{"title":"Electronic charge density distortions due to dispersion: Physically meaningful DMA multipoles for H2, HeH, and He···He","authors":"Nathan Jansen, Hua-Kuang Lee, Katharine Clarke Hunt","doi":"10.1039/d5cp01955a","DOIUrl":"https://doi.org/10.1039/d5cp01955a","url":null,"abstract":"Feynman attributed long-range dispersion forces to the attraction of each nucleus to the local dipolar distortion of the electronic charge distribution. Here we take a step toward the first demonstration of Feynman’s statement with full configuration-interaction wave functions. We have used Stone’s distributed multipole analysis (DMA) to obtain the local multipoles in H2 in the b3Σu+ and X1Σg+ states and the local dipoles for in HeH and He···He in their ground states. These states have repulsive potentials with shallow wells due to van der Waals dispersion. For H2, the DMA dispersion dipole on each nucleus, computed abinitio with the d-aug-cc-pV6Z basis, shows excellent agreement with the sum of the R-7 and R-9 terms predicted by perturbation theory. The DMA dipoles of HeH and He···He also agree quite well the prediction of perturbation theory. The signs and the R-dependence of the DMA dispersion dipoles are fully consistent with Feynman’s statement. For H2, we also find strong agreement between the results of perturbation theory and the dispersion terms in the DMA quadrupoles, DMA octopoles, DMA hexadecapoles, the total quadrupoles, and the total hexadecapoles. The dynamic correlation effects on the multipoles have physical meaning when computed with sufficiently large basis sets.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"11 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203107","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

Boron-Doped ZrS2 Monolayer as a Promising Gas Sensing Material for the Detection of Volatile Organic Compounds: A DFT Study 掺硼ZrS2单层作为一种有前途的气体传感材料用于挥发性有机物的检测：DFT研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp03083h

Xiao-Qian Lin, Zhen-Hong Han, Xin Zhang, Jin-Xia Yang, Yuan-Gen Yao

{"title":"Boron-Doped ZrS2 Monolayer as a Promising Gas Sensing Material for the Detection of Volatile Organic Compounds: A DFT Study","authors":"Xiao-Qian Lin, Zhen-Hong Han, Xin Zhang, Jin-Xia Yang, Yuan-Gen Yao","doi":"10.1039/d5cp03083h","DOIUrl":"https://doi.org/10.1039/d5cp03083h","url":null,"abstract":"Detecting volatile organic compounds (VOCs) with high sensitivity and selectivity is essential for environmental monitoring and health protection. This study employs first-principles calculations to explore the structural, electronic, and adsorption properties of pristine and boron-doped ZrS2 (B-ZrS2) monolayers toward key VOCs: formaldehyde (CH2O), methanol (CH3OH), acetaldehyde (CH3CHO), and acetone (C3H6O). Boron atoms stably incorporate at hollow sites, forming strong covalent B–S bonds and significantly narrowing the band gap from 0.861 eV to 0.091 eV. Pristine ZrS2 exhibits weak physisorption and minimal charge transfer with VOCs, limiting sensing capability. In contrast, B doping creates chemically active sites that promote chemisorption through B–O bond formation and enhanced charge transfer. Density of states analyses reveal strong electronic coupling between adsorbates and the B-ZrS2 surface, causing notable electronic structure changes. Frontier molecular orbital theory shows that VOC adsorption increases the band gap, reducing electrical conductivity and modulating the sensor signal. Calculated sensitivities indicate that B-ZrS2 responds effectively to all four VOCs at room temperature, especially methanol, with rapid recovery facilitated by temperature-dependent desorption kinetics. Additionally, B-ZrS2 shows weak interactions with common atmospheric gases (N2, O2, CO2, H2O), ensuring selectivity and stable sensor performance under realistic conditions. Overall, these results demonstrate that B-ZrS2 is a promising, sensitive, selective, and thermally adaptable resistive-type gas sensor for environmental VOCs detection.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"8 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203144","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

A Reduced-Parameter Variational Strategy for Accelerated Evaluation of Thermal Density Matrices via Quantum Effective Harmonic Oscillators Approach 利用量子有效谐振子方法加速热密度矩阵计算的降参数变分策略

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp02844b

Mokshi Sharma, Tapta Kanchan Roy

{"title":"A Reduced-Parameter Variational Strategy for Accelerated Evaluation of Thermal Density Matrices via Quantum Effective Harmonic Oscillators Approach","authors":"Mokshi Sharma, Tapta Kanchan Roy","doi":"10.1039/d5cp02844b","DOIUrl":"https://doi.org/10.1039/d5cp02844b","url":null,"abstract":"Accurate treatment of anharmonic and temperature-dependent quantum effects is crucial for the reliable evaluation of thermal density matrices and vibrational partition functions, which in turn affect the accuracy of thermodynamic and spectroscopic predictions. In this study, a McLachlan-type variational principle based on the Bloch equation is developed for the calculation of the thermal density matrices and the associated vibrational partition function. Quantum anharmonic effects are captured through the independent-particle Effective Harmonic Oscillator (EHO) approximation, in which vibrational wave functions are defined solely by two variational parameters: the centroids and widths of multidimensional Gaussian product functions. The proposed variational method optimizes the trace of the squared deviation between the derivatives of the exact and model density matrices with respect to the parameters of the model Hamiltonian. The accuracy and efficiency of this Bloch equation based thermal-EHO (TB-EHO) approach are evaluated by calculating the thermal properties of various molecular systems, and comparing the results with those from the thermal vibrational configuration interaction (T-VCI) and earlier proposed Bloch equation based thermal vibrational self-consistent field (TB-VSCF) methods as benchmarks. The TB-EHO method yields results that closely match the reference values across a wide temperature range (0 to 1000 K). The approach is further validated by computing the equilibrium constant for a cis-trans isomerization reaction, yielding results in good agreement with TB-VSCF and experimental data. Moreover, the TB-EHO method exhibits substantial computational efficiency, reducing CPU time by ~98% compared to the TB-VSCF, making it highly suitable for applications to large molecular systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"32 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203146","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Deep learning interatomic potential for boron phosphide: accurate prediction of mechanical and thermal properties 磷化硼的深度学习原子间势：机械和热性能的准确预测

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp01433f

Kai Ren, Chao Lv, Yang Wang, Chao Zhang, Dongqi Wang

{"title":"Deep learning interatomic potential for boron phosphide: accurate prediction of mechanical and thermal properties","authors":"Kai Ren, Chao Lv, Yang Wang, Chao Zhang, Dongqi Wang","doi":"10.1039/d5cp01433f","DOIUrl":"https://doi.org/10.1039/d5cp01433f","url":null,"abstract":"Boron phosphide (BP) is a promising high temperature thermoelectric material with good thermal stability and chemical inertness. Recently, interatomic potentials based on machine learning methods with neural networks have attracted a lot of attention due to their high accuracy and efficiency in atomistic simulations. In this work, a deep potential (DP) of BP was trained using machine learning (ML) methods. The structure and properties of BP were investigated using the trained DP. It was found that that the DP simulation accurately reproduces the radial and angular distribution functions of BP, and that the lattice constants and density are in good agreement with the first-principles calculations and experimental results. It accurately reproduces key physical properties of boron phosphide, including radial and angular distribution functions, lattice constants, density, structural properties, mechanical properties (such as elastic constants and hardness), fracture toughness, and thermal properties (such as entropy, enthalpy, free energy, heat capacity, thermal conductivity, and phonon spectrum). These results show that the trained BP deep learning potential can accurately describe BP materials.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"28 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203111","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

Correction: Square octagon haeckelites as efficient photocatalysts with enhanced solar-to-hydrogen conversion and high carrier mobilities 更正：方形八角形海蚀石是高效的光催化剂，具有增强的太阳能到氢转化和高载流子迁移率

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp90174j

Ismail Shahid, Iqtidar Ahmad, Anwar Ali, Abid Raza, Xiaoliang Zhang, Dawei Tang, Mohamed Kallel, Shaimaa A. M. Abdelmohsen

引用次数: 0

Explainable GNN-Derived Structure-Property Relationships in Interstitial-Alloy Materials 间隙合金材料中可解释的gnn衍生的结构-性能关系

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-01 DOI: 10.1039/d5cp02208h

Eduardo Aguilar-Bejarano, Luis Arrieta, Mauricio Gutiérrez, Ender Özcan, Simon Woodward, Grazziela Figueredo, J. Ignacio Borge

{"title":"Explainable GNN-Derived Structure-Property Relationships in Interstitial-Alloy Materials","authors":"Eduardo Aguilar-Bejarano, Luis Arrieta, Mauricio Gutiérrez, Ender Özcan, Simon Woodward, Grazziela Figueredo, J. Ignacio Borge","doi":"10.1039/d5cp02208h","DOIUrl":"https://doi.org/10.1039/d5cp02208h","url":null,"abstract":"This study presents a novel approach to understanding the structure-property relationships in non-stoichiometric materials and interstitial alloys using Graph Neural Networks (GNNs). Specifically, we apply the Crystal Graph Convolutional Network (CGCNet) to predict the properties of transition-metal carbides, Mo$_2$C and Ti$_2$C, and introduce the Crystal Graph Explainer (CGExplainer) enabling model interpretability. CGCNet outperforms traditional human-derived interatomic potential models (IAPs) in prediction accuracy and data efficiency, with significant improvements in the ability to extrapolate properties to larger supercells. Additionally, the CGExplainer tool enables detailed analysis of the relative spatial positioning of atomic ensembles, revealing key atomic arrangements that govern material properties. This work highlights the potential of GNN-based approaches for rapidly discovering complex structure-property relationships and accelerating the design of materials with customized properties, particularly for alloys with variable atomic compositions. Our methodology offers a robust framework for future materials discovery, extending the applicability of GNNs to a broader range of materials systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"10 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203148","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

Seeking Metal-Organic Frameworks for hydrogen storage using classical and quantum active learning 利用经典和量子主动学习寻找储氢的金属有机框架

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-01 DOI: 10.1039/d5cp02747k

Maicon Pierre Lourenço, Rishabh Shukla, Daya Gaur, Utkarsh Singh, Dennis Salahub, Mosayeb Naseri, Sergey Gusarov

{"title":"Seeking Metal-Organic Frameworks for hydrogen storage using classical and quantum active learning","authors":"Maicon Pierre Lourenço, Rishabh Shukla, Daya Gaur, Utkarsh Singh, Dennis Salahub, Mosayeb Naseri, Sergey Gusarov","doi":"10.1039/d5cp02747k","DOIUrl":"https://doi.org/10.1039/d5cp02747k","url":null,"abstract":"Metal-organic frameworks (MOFs) are porous materials with applications from chemical sensing to gas storage and separation. The development of MOFs for hydrogen storage is highly desired. Hydrogen is a clean source of energy and storing it within MOFs depends on their structure, stability, synthesis design and adsorption characteristics. The design space to obtain MOFs with suitable target properties can be aided by artificial intelligence methods that use few data for new discovery, such as active learning (AL) and the recent quantum AL (QAL) method. In this work, AL and QAL methods for MOF design were developed and tested in the search for MOFs and experimental conditions (temperature and pressure) that have enhanced hydrogen storage capability. Our aim is to explore the performance of these techniques in finding this optimum material within a known MOF data set. The AL methods investigated in this work use artificial neural network, support vector regression, classical and quantum Gaussian process (GP and QGP) as regression models for inference. Different uncertainty quantifications for the regression models were considered as well as different acquisition functions for decision making: to select the next MOF to be measured by further \"experiments\". The QAL performance in finding the optimum material and experimental conditions is reported. QAL uses QGP with a projected quantum kernel with a feature map with entanglement. A network graph method was developed to analyze the AL and QAL performance for MOFs search. The AL and QAL results applied in this known data set indicate that it is possible to search for MOFs with enhanced properties for hydrogen storage with very few data, being able to distinguish the optimum MOF and conditions from similar ones. This finding highlights the potential of classical and quantum \"machines\" (i.e.: AL and QAL methods) to indicate new MOFs to be synthesized with enhanced adsorption properties.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"71 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194936","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

Study on the electronic structure and mechanical stability of three TiO2/CeO2 interfaces for high-quality and efficient polishing of core-shell abrasive 高质量高效抛光核壳磨料的三种TiO2/CeO2界面电子结构和机械稳定性研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-01 DOI: 10.1039/d5cp03655k

Huiling Jia, Jie Zhang, Xinze Zhang, Xin Tan, Yanan Cao

{"title":"Study on the electronic structure and mechanical stability of three TiO2/CeO2 interfaces for high-quality and efficient polishing of core-shell abrasive","authors":"Huiling Jia, Jie Zhang, Xinze Zhang, Xin Tan, Yanan Cao","doi":"10.1039/d5cp03655k","DOIUrl":"https://doi.org/10.1039/d5cp03655k","url":null,"abstract":"Due to the problems of easy agglomeration and high polishing defect rate of the single CeO2 particle, this study constructed a core-shell structured TiO2/CeO2 composite abrasive with the aim of achieving high-quality and efficient polishing. In this study, the core-shell TiO2/CeO2 composite abrasive was constructed to achieve high-quality and efficient polishing. The atomic structure, electronic structure, and mechanical property of a-TiO2(001)/CeO2(001), a-TiO2(101)/CeO2(111) and r-TiO2(110)/CeO2(111) interfaces and their interfaces containing O vacancy were studied using first principles calculations. The results indicated that the structure stability of three TiO2/CeO2 interfaces was determined by the number and length of Ti-O and Ce-O covalent bonds generated in the interface region. The adhesion work of the stable a-TiO2(001)/CeO2(001) interface and the most unstable r-TiO2(110)/CeO2(111) interface were 2.28 and 0.53 J/m2, respectively. Oxygen vacancy defects reduced the adhesion work and ideal shear strength of three TiO2/CeO1.94 interfaces. The fracture of Ti-O bonds in the interface region was the reason for the failure of the a-TiO2(001)/CeO2(001) and a-TiO2(101)/CeO1.94(111) interfaces, while the failure of other interfaces was mainly caused by the fracture of Ce-O bonds in the interface region. Under shear strain, the chemical activities of the r-TiO2(110)/CeO2(111) and r-TiO2(110)/CeO1.94(111) interfaces were reduced.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"65 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194938","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