Physical Chemistry Chemical Physics最新文献_第10页

Impact of Ce doping on the optoelectronic and structural properties of a CsPbIBr2 perovskite solar cell Ce掺杂对CsPbIBr2钙钛矿太阳能电池光电性能和结构性能的影响

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-23 DOI: 10.1039/d5cp02196k

Muhammad Iftikhar Khan, Ali Mujtaba, Mahvish Fatima, Riadh Marzouki, Saddam Hussain, Tauseef Anwar

引用次数: 0

Mechanistic Insights into Fe-M Dual-Metal-Site Catalysts for the Oxygen Reduction Reaction Fe-M双金属位催化剂氧还原反应机理研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-23 DOI: 10.1039/d5cp01857a

Can Deng, Chaofang Deng

{"title":"Mechanistic Insights into Fe-M Dual-Metal-Site Catalysts for the Oxygen Reduction Reaction","authors":"Can Deng, Chaofang Deng","doi":"10.1039/d5cp01857a","DOIUrl":"https://doi.org/10.1039/d5cp01857a","url":null,"abstract":"Introducing transition metals adjacent to the Fe site in Fe-N-C single-atom catalysts to construct double-atom catalysts (DACs) presents a promising strategy for enhancing the performance of the oxygen reduction reaction (ORR). However, the understanding of the catalytic mechanisms of DACs remains controversial， thereby hindering the rational design of ideal DACs. In this work, we constructed seven iron-metal-nitrogen-carbon catalysts (note as Fe-M@NC, M = Cr、 Mn、 Fe、 Co、 Ni、 Cu、 Zn) to gain in-depth insights into the catalytic mechanisms. We found that Fe-Fe@NC and Fe-Co@NC exhibit superior ORR activity compared to the other constructed catalysts, featuring higher limiting potentials of 1.081 V and 0.888 V, respectively. Detailed reaction mechanism analysis revealed that, in the absence of potential effects, ORR on these two catalysts follows a dissociative pathway. By contrast, when potential was considered, they catalyze ORR via the associative mechanism. This discrepancy arises because O2 adsorption energy weakens under uniform potential conditions, which is unfavorable for direct cleavage of the O=O bond. Therefore, it manifests as the associate mechanism. Under this mechanism, the limiting potentials of these DACs are both around 0.9 V, consistent with the experimental results. Additionally, the adsorption energies of other ORR intermediates also exhibit nonlinear dependence on electrode potential. This study demonstrates the advantages of Fe-Fe@NC and Fe-Co@NC catalysts in ORR and emphasizes the critical role of potential effects in understanding catalyst activity and reaction mechanisms.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"667 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684574","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

Machine learning based prediction of MnO2 cathode discharge capacity for high-performance zinc-ion batteries. 基于机器学习的高性能锌离子电池MnO2阴极放电容量预测。

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-23 DOI: 10.1039/d5cp01218j

Nure Alam Chowdhury,Leaford Nathan Adebayo Henderson,Samin Yaser,Olusola Pelumi Oyeku,Maydenee Maydur Tresa,Chandra Kundu,Jayan Thomas

{"title":"Machine learning based prediction of MnO2 cathode discharge capacity for high-performance zinc-ion batteries.","authors":"Nure Alam Chowdhury,Leaford Nathan Adebayo Henderson,Samin Yaser,Olusola Pelumi Oyeku,Maydenee Maydur Tresa,Chandra Kundu,Jayan Thomas","doi":"10.1039/d5cp01218j","DOIUrl":"https://doi.org/10.1039/d5cp01218j","url":null,"abstract":"Zinc-ion batteries (ZIBs) are considered as a cheaper, non-toxic and safer alternative to lithium-ion batteries (LIBs). Manganese dioxide (MnO2) is one of the most viable cathode materials for aqueous electrolyte based ZIBs. The addition of different dopants in the MnO2 cathode material can significantly change its physical properties and electrochemical performance in ZIBs. In this study, we collected about 603 papers from which we selected 57 ZIB published papers related to doped MnO2 as a cathode material. The dataset consists of a total of eleven features (ten input features and one target) in which six features are related to battery properties and five features are related to the elemental properties of the dopants. The Pearson correlation plot is considered to investigate the correlation between different features, and it is observed that the electronegativity and first-ionization energy of the dopant have a positive relation with discharge capacity (DC). Both classification and regression treatment are applied to our dataset using different machine learning models such as XGBoost, random forest (RF), and K-nearest Neighbors. The RF model can classify DC with an accuracy of 0.72 into three predefined grades. In the regression analysis, the XGBoost model can predict DC with an R2 value of 0.92. Finally, the findings of this study can be utilized to predict the performance of doped MnO2 before synthesizing it in the laboratory.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"15 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684125","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 Thermodynamic Assessment of the Decomposition and Rehydrogenation of o1-Ba(BH4)2 based on DFT Calculations and Correlation Functions 基于DFT计算和相关函数的o1-Ba(BH4)2分解和再加氢热力学评价

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-23 DOI: 10.1039/d5cp00744e

Konrad Jörg Burkmann, Markus Mehlhorn, Angus Demmer, Jakob Kraus, Franziska Habermann, Jürgen Seidel, Klaus Bohmhammel, Jens Kortus, Florian Oliver Mertens

{"title":"A Thermodynamic Assessment of the Decomposition and Rehydrogenation of o1-Ba(BH4)2 based on DFT Calculations and Correlation Functions","authors":"Konrad Jörg Burkmann, Markus Mehlhorn, Angus Demmer, Jakob Kraus, Franziska Habermann, Jürgen Seidel, Klaus Bohmhammel, Jens Kortus, Florian Oliver Mertens","doi":"10.1039/d5cp00744e","DOIUrl":"https://doi.org/10.1039/d5cp00744e","url":null,"abstract":"In this study, an estimate is given for the enthalpy of formation at 298.15 K for the room temperature phase of barium boranate, o1-Ba(BH4)2, based on correlations between well known enthalpies of formation of boranates and the corresponding values of the respective metal perchlorates and bromides as well as the electronegativity according to Pauling. A new procedure for estimating the absolute entropy at 298.15 K using metal bromides is presented as well. To evaluate this method, the absolute entropy value at 298.15 K was calculated from the Gibbs free energy function of o1-Ba(BH4)2. The Gibbs free energy function and corresponding heat capacity values between SI{5}{K} and SI{700}{K} were calculated applying density functional theory (DFT) and statistical thermodynamics using the quasi-harmonic approach. Furthermore, several thermodynamic calculations regarding possible synthesis reactions and decomposition routes of o1-Ba(BH4)2 are discussed.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"110 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684571","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

Substituent Effects in a Six-State Molecular Switch 六态分子开关中的取代基效应

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-23 DOI: 10.1039/d5cp02098k

Rachael Hannah, Kirsten van der Geest, Shahrzad Shafei, Ben L. Feringa, Ryan Chiechi

引用次数: 0

Solvent-dimer-mediated clusters as a microscopic model of solution: IR spectroscopy and density functional theory of jet-cooled pyrrole-tetrahydrofuran clusters. 溶剂-二聚体介导的团簇作为溶液的微观模型：喷气冷却吡咯-四氢呋喃团簇的红外光谱和密度泛函理论。

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-23 DOI: 10.1039/d5cp02058a

Yoshiteru Matsumoto,Yukino Yamada

{"title":"Solvent-dimer-mediated clusters as a microscopic model of solution: IR spectroscopy and density functional theory of jet-cooled pyrrole-tetrahydrofuran clusters.","authors":"Yoshiteru Matsumoto,Yukino Yamada","doi":"10.1039/d5cp02058a","DOIUrl":"https://doi.org/10.1039/d5cp02058a","url":null,"abstract":"A solvated cluster in a supersonic jet serves as a microscopic model of a bulk solution. Generally, a 1-1 cluster of an organic solute with a simple solvent molecule is considered the smallest solvated cluster. However, a bulk solution consists of a solute surrounded by multiple solvent molecules. Therefore, the smallest solvated cluster is practically a 1-2 cluster comprised of one solute and two solvents, allowing us to investigate intermolecular interactions not only between the solute and the solvent but also among the solvents themselves. In this study, we focus on solvent-dimer-mediated clusters of pyrrole (Py) and tetrahydrofuran (THF) dimers to elucidate the mechanism of micro-solvation. The solvation structures of Py-THF clusters are determined through a combination of IR cavity ringdown spectroscopy and density functional theory computations. The hydrogen-bonded structures of Py1-THF1, Py2-THF1, and Py1-THF2 are analyzed in terms of the geometric deformation of the THF backbone. Notably, we found that the geometric deformation of the solvent THF dimer in Py1-THF2 is significantly larger than that of the other solvent dimers. To discuss the relationship between the deformation of the solvent dimer and the solubility of the bulk solution, we introduced Hansen Solubility Parameters. Consequently, we concluded that the flexible solvation by a solvent dimer, due to its large deformation, correlates with higher solubility in a bulk solution. The concept of solvent-dimer-mediated clusters preliminarily provides new insights into connecting micro-solvation with macro-solutions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"14 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684126","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

Implementation of quasiclassical mapping approaches for nonadiabatic molecular dynamics in the PySurf package 在PySurf包中实现非绝热分子动力学的准经典映射方法

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-23 DOI: 10.1039/d5cp01194a

David Picconi, Maximilian Friedrich S. J. Menger, Elisa Palacino-González, Edison Xavier Salazar, Shirin Faraji

{"title":"Implementation of quasiclassical mapping approaches for nonadiabatic molecular dynamics in the PySurf package","authors":"David Picconi, Maximilian Friedrich S. J. Menger, Elisa Palacino-González, Edison Xavier Salazar, Shirin Faraji","doi":"10.1039/d5cp01194a","DOIUrl":"https://doi.org/10.1039/d5cp01194a","url":null,"abstract":"Quasiclassical methods for nonadiabatic molecular dynamics, based on the Mayer-Miller-Stock-Thoss mapping, are implemented in the open source computer package PySurf. This complements the implementation of surface hopping approaches performed in previous works, and leads to a unified code that allows nonadiabatic dynamics simulations using various mapping approaches (Ehrenfest dynamics, the linearized semiclassical initial value representation, the Poisson-bracket mapping equation, the “unity” approach for the indentity operator, the spin mapping, and the symmetrical quasiclassical windowing method) as well as different flavours of surface hopping (fewest-switches, Landau-Zener, and a mapping-inspired scheme). Furthermore, a plugin is developed to provide diabatic vibronic models in a sum-of-products form. This opens the way to the benchmark of different types of trajectory-based propagators on different models, against exact quantum dynamical simulations performed, e.g., by the multiconfigurational time-dependent Hartree method. Illustrative calculations, performed using the whole set of available propagators, are presented for different harmonic and anharmonic two-state models, exhibiting various degrees of correlation between vibrational modes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"33 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144685037","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

H-Bonding-Assisted Energy Retention in Bicyclic Diene Photoswitches for Rechargeable Solar Thermal Batteries: CASSCF, CASPT2, and DLPNO-CCSD(T) Insights 用于可充电太阳能热电池的双环二烯光开关的h键辅助能量保留：CASSCF， CASPT2和DLPNO-CCSD(T)见解

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-23 DOI: 10.1039/d5cp01525a

Akanksha Ashok Sangolkar, Rama Krishna Kadiyam, Sibam Sahu, Ravinder Pawar

{"title":"H-Bonding-Assisted Energy Retention in Bicyclic Diene Photoswitches for Rechargeable Solar Thermal Batteries: CASSCF, CASPT2, and DLPNO-CCSD(T) Insights","authors":"Akanksha Ashok Sangolkar, Rama Krishna Kadiyam, Sibam Sahu, Ravinder Pawar","doi":"10.1039/d5cp01525a","DOIUrl":"https://doi.org/10.1039/d5cp01525a","url":null,"abstract":"Molecular solar thermal (MOST) systems have potential to harness and store vast amount of solar energy and promises for renewable energy solutions. However, the integration of solar absorption, high energy storage density, and long thermal half-life into a single photochromic couple remains a contemporary challenge, hindering their practical deployment. In this work, we present a rational design strategy to enhance key properties of a bridged bicyclic diene (BBD)-based photoswitch through elongation of the unsaturated bridge and strategic functionalization. The introduced substituents promote synergistic non-covalent interactions, particularly intramolecular hydrogen bonding and reinforce push–pull electronic effects, collectively enabling pronounced bathochromic shifts in absorption without compromising energy storage capacity and duration. Comprehensive electronic structure analyses carried out using CASSCF, CASPT2, and DLPNO-CCSD(T) methods ensure the robustness of the findings. This study provides valuable design principles for next-generation MOST systems by leveraging the cooperative effects of non-covalent interactions and electronic modulation through functionalization.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"4 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684575","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

Phase transition and in-plane anisotropy of GeAs under high pressure 高压下GeAs的相变及面内各向异性

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-23 DOI: 10.1039/d5cp01462j

Junbo Wang, Zilong Zhang, Shiquan Feng, Haining Li, Xiang Zhu, Kun Yang, Xuerui Cheng

{"title":"Phase transition and in-plane anisotropy of GeAs under high pressure","authors":"Junbo Wang, Zilong Zhang, Shiquan Feng, Haining Li, Xiang Zhu, Kun Yang, Xuerui Cheng","doi":"10.1039/d5cp01462j","DOIUrl":"https://doi.org/10.1039/d5cp01462j","url":null,"abstract":"GeAs exhibits excellent chemical stability and high in-plane anisotropy at ambient conditions. Pressure is one effective approach to discover and access new structure or novel properties for 2D materials. In this work, the high-pressure effect on the phase transition and in-plane anisotropic property is investigated for GeAs using Raman spectroscopy, infrared spectroscopy, high-pressure resistance, and density functional theory. Results show that GeAs undergoes an irreversible monoclinic-to-cubic transition around 18.4 GPa during compression. IR and resistivity measurements indicate this cubic rock-salt structure exhibits a metallic state. Upon decompression, high pressure cubic GeAs converts to a tetragonal structure rather than the initial monoclinic structure. Moreover, tetragonal GeAs also exhibits a metallic state. This transition is reversible, that tetragonal GeAs will convert back to cubic GeAs around 18.2 GPa. Angle-resolved polarized Raman spectroscopy reveal that for both Ag and Bg modes of monoclinic GeAs, pressure will induce a 10°-15° deflection for their polarization direction up to 10 GPa, but has no effect on their anisotropy periods. Tetragonal GeAs also exhibits excellent in-plane optical anisotropy with a period of 180°. But different from monoclinic GeAs, both polarization direction and periods keep stable for its Raman mode under pressure. The result is conducive to understanding the structural stability and anisotropic properties of GeAs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"99 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684572","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

Probing the adsorption behavior of triphenylphosphine oxide on the surface of Ga–SiO2 with different binding sites 探究三苯基氧化膦在不同结合位点的Ga-SiO2表面的吸附行为

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-22 DOI: 10.1039/d5cp00793c

Yonggang Yang, Chenhao Zheng, Yang Liu, Zhinan Jiang, Tiantian Guan, Chunsheng Zhuang, Yufang Liu

{"title":"Probing the adsorption behavior of triphenylphosphine oxide on the surface of Ga–SiO2 with different binding sites","authors":"Yonggang Yang, Chenhao Zheng, Yang Liu, Zhinan Jiang, Tiantian Guan, Chunsheng Zhuang, Yufang Liu","doi":"10.1039/d5cp00793c","DOIUrl":"https://doi.org/10.1039/d5cp00793c","url":null,"abstract":"This study theoretically investigates the adsorption dynamics and fluorescence characteristics of triphenylphosphine oxide (TPPO) as a fluorescent probe on Lewis acid (Ga–La) and Brønsted acid (Ga–Ba) sites of gallium silicate (Ga–SiO2) surfaces. It was determined that TPPO binds to the Ga–La site via a coordination bond and to the Ga–Ba site through a hydrogen bond. When excited to the first singlet (S1) state, the coordination interactions at the Ga–La sites experienced slight weakening, which caused a blue shift in the fluorescence emission of TPPO from 478 nm to 453 nm. The excited state intermolecular proton transfer occurring at the Ga–Ba site leads to a red shift of the TPPO fluorescence peak to 528 nm. The contrasting fluorescence behaviors provide a sensitive probe for distinguishing Ga–La and Ga–Ba sites, advancing the detection and mechanistic understanding of Ga–SiO2's catalytic acid centers. This work highlights the potential of fluorescence spectroscopy in elucidating surface-active sites for catalysis.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"52 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144678227","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