Physical Chemistry Chemical Physics最新文献_第2页

Molecular Scale Understanding on the Oil-Water-Calcite Wettability: Role of Acid Component and Effect of CO2 分子尺度对油水方解石润湿性的认识：酸组分的作用和CO2的影响

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-08-01 DOI: 10.1039/d5cp01840d

Yu Zhao, Yunfeng Liang, Takeshi Tsuji, Shinsuke Mochizuki, Fei Jiang

{"title":"Molecular Scale Understanding on the Oil-Water-Calcite Wettability: Role of Acid Component and Effect of CO2","authors":"Yu Zhao, Yunfeng Liang, Takeshi Tsuji, Shinsuke Mochizuki, Fei Jiang","doi":"10.1039/d5cp01840d","DOIUrl":"https://doi.org/10.1039/d5cp01840d","url":null,"abstract":"Carbon Capture, Utilization, and Storage (CCUS) is a critical strategy for climate change mitigation, often involving CO2 injection into carbonate reservoirs for Enhanced Oil Recovery (EOR) and geological storage. Reservoir wettability significantly impacts these processes, yet carbonate formations frequently become oil-wet due to organic acid adsorption from crude oil, hindering recovery. While CO2 injection can alter wettability towards a more favorable water-wet state, the underlying molecular mechanisms involving CO2, adsorbed organic acids, and the calcite surface are not fully understood. This study employs Molecular Dynamics (MD) simulations to elucidate these mechanisms, using butyric acid as a model acidic component. Results demonstrate that CO2 significantly enhances the hydrophilicity of the calcite surface initially rendered partially lipophilic by butyric acid adsorption (water droplet contact angle increased from 0° to 29°). The addition of CO2 reduced the contact angle back to 8°, restoring hydrophilicity. This wettability shift is attributed to a competitive adsorption mechanism where sufficient concentrations of CO2 displace butyric acid from the calcite surface. This displacement is facilitated by the formation of hydrogen bonds between CO2 molecules and the carboxyl groups of the butyric acid, disrupting the acid's interaction with the calcite. By clarifying this interplay among CO2, acidic components, and the calcite surface, this work provides fundamental, molecular-scale insights into interfacial phenomena. These findings can guide the optimization of CO2-EOR efficiency and advance CCUS applications in carbonate reservoirs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"146 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144756567","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

Delayed photoisomerisation of the trans-PSB3 retinal toy model using on-the-fly quantum dynamics 利用动态量子动力学研究反式psb3视网膜玩具模型的延迟光异构化

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-08-01 DOI: 10.1039/d5cp02117k

María Mallo, Susana Gómez-Carrasco, Sandra Gómez

引用次数: 0

Strain-Tunable MoSe2/ZrCl2 Heterostructures: First-Principles Insights into Photoegalvanic and Switching Device Performance 应变可调谐MoSe2/ZrCl2异质结构：光等化和开关器件性能的第一性原理见解

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-08-01 DOI: 10.1039/d5cp02174j

Zhonghui Xu, HongYang Yu, Bing Luo, Guogang Liu, Jiaxin Lu, Jie Kang

{"title":"Strain-Tunable MoSe2/ZrCl2 Heterostructures: First-Principles Insights into Photoegalvanic and Switching Device Performance","authors":"Zhonghui Xu, HongYang Yu, Bing Luo, Guogang Liu, Jiaxin Lu, Jie Kang","doi":"10.1039/d5cp02174j","DOIUrl":"https://doi.org/10.1039/d5cp02174j","url":null,"abstract":"Two-dimensional (2D) heterostructure materials, known for their tunable multifunctionality and low-dimensional confinement effects, offer vast potential for diverse applications. This work provides a comprehensive investigation of the electronic structure, transport and optical properties of MoSe2/ZrCl2 heterostructures using density functional theory (DFT) with non-equilibrium Green's function (NEGF) methods. Our results demonstrate that the electronic properties of MoSe2/ZrCl2 heterostructure materials can be precisely tuned by applying biaxial strain. Specifically, biaxial strain triggers a semiconductor-to-metal transition and modulates the bandgap from direct to indirect. In addition, we found that the MoSe2/ZrCl2 heterostructure exhibits remarkable optical properties with pronounced absorption peaks in the visible and near-ultraviolet regions. Photodetector simulations reveal substantial photocurrents in the visible range, particularly within the 1.6-3.6 eV photon energy regions, where distinct photocurrent peaks are observed. In addition, the MoSe2/ZrCl2heterostructure based device exhibits exceptional photodetector performance, with a current switching ratio reaching 1010 at +8% biaxial strain. In summary, our study highlights the ability to finely tune the electronic and optical properties of MoSe2/ZrCl2heterostructures through biaxial strain, offering promising prospects for the development of MoSe2/ZrCl2-based nano-switching and optoelectronic devices in practical applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"11 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144756568","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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Molecular Packing-Dependent Thermal Decomposition Pathways in 3,4-Dinitrofurazanfuroxan: Insights from SCC-DFTB Molecular Dynamics Simulations 分子包装相关的3,4-二硝基呋喃呋喃嘧啶热分解途径：来自SCC-DFTB分子动力学模拟的见解

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-08-01 DOI: 10.1039/d5cp01115a

Shuang-Fei Zhu, Fangfang Hou, Jinxuan Xuan, Rui-Jun Gou, Shu-hai Zhang, Shang-biao Feng, Yang Liu

{"title":"Molecular Packing-Dependent Thermal Decomposition Pathways in 3,4-Dinitrofurazanfuroxan: Insights from SCC-DFTB Molecular Dynamics Simulations","authors":"Shuang-Fei Zhu, Fangfang Hou, Jinxuan Xuan, Rui-Jun Gou, Shu-hai Zhang, Shang-biao Feng, Yang Liu","doi":"10.1039/d5cp01115a","DOIUrl":"https://doi.org/10.1039/d5cp01115a","url":null,"abstract":"This work investigates the influence of molecular packing arrangements on the initial thermal decomposition mechanisms of 3,4-dinitrofurazanfuroxan (DNTF) using self-consistent charge density functional tight-binding (SCC-DFTB) molecular dynamics simulations. Ordered and disordered DNTF models were constructed and subjected to programmed heating (300~3000 K) and constant temperature heating conditions (2000 K, 2500 K, 3000 K). The ordered model exhibited diverse decomposition pathways, including nitro group dissociation (R5) and multiple N-O bond cleavages (R1–R4), while the disordered model predominantly followed the low-energy-barrier R1 pathway (central ring N-O cleavage). Potential energy analysis revealed higher energy peaks and faster decomposition kinetics in the ordered configuration. Fragment evolution profiles demonstrated distinct decomposition mechanisms: the disordered model favored furoxan ring-opening, whereas the ordered model preferentially decomposed nitrofurazan rings. Additionally, the disordered model exhibited earlier decomposition onset but slower kinetics compared to the ordered system. These findings highlight the critical role of molecular packing in modulating thermal stability and decomposition pathways, providing insights for optimizing the safety and performance of melt-cast explosives.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"36 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144756569","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

Transfer learning with domain knowledge adaptation for stability evaluation of dual-atom catalysts on nitrogen-doped carbon 应用领域知识自适应迁移学习评价氮掺杂碳双原子催化剂的稳定性

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-08-01 DOI: 10.1039/d5cp01340b

Maria G. Minotaki, Núria López

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Cavity mediated enhancement of CISS in DNA junctions 空腔介导的CISS在DNA连接中的增强

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-08-01 DOI: 10.1039/d5cp02200b

Anqi Li, Michael Galperin

引用次数: 0

Size matching and electrostatic potential as complementary methods for understanding the metallic cluster configurations inside fullerenes 尺寸匹配和静电势作为理解富勒烯内部金属团簇结构的互补方法

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-08-01 DOI: 10.1039/d5cp01717c

Chenliang Pan, Shuaijiang Liu, Peng Jin

{"title":"Size matching and electrostatic potential as complementary methods for understanding the metallic cluster configurations inside fullerenes","authors":"Chenliang Pan, Shuaijiang Liu, Peng Jin","doi":"10.1039/d5cp01717c","DOIUrl":"https://doi.org/10.1039/d5cp01717c","url":null,"abstract":"The size matching between internal cluster and outer cage is widely used to explain the former’s configuration in endohedral clusterfullerenes (ECFs). For example, the trimetallic nitride (M3N) clusters within smaller fullerenes are expected to become more relaxed in larger ones due to the alleviative cage confinement. However, recent single-crystal X-ray diffraction (SCXRD) experiments reveal that, although being planar in C80, the Sc3N cluster exhibits an abnormal pyramidal shape in Cs(51365)-C84 and D3(19)-C86. Such a phenomenon is explained by the “spider effect” occurred when a small cluster meets a large cage. Herein, to further solve this puzzle and deeply understand the internal cluster configurations of ECFs, density functional theory calculations were conducted for all nine SCXRD characterized Sc3N@C2n (2n = 68, 70, 78-86) nitride clusterfullerenes. After well reproducing their structural characteristics, we found that all their cluster configurations can be rationalized by the electrostatic potentials (ESPs) inside corresponding C2n6- anionic empty cages. These cage anions exhibit rather different ESPs distributions, and the intramolecular host-guest electrostatic interactions drive the three Sc3+ cations approach to the more negative region, whereas the central N3- anion to the less negative one, thus resulting in the planar or slightly pyramidal shape of the whole (Sc3N)6+ unit. Moreover, besides these nitride ECFs, ESPs can explain the internal cluster configurations of other types of ECFs as well. Different from the conventional viewpoint which only focuses on the cluster and cage sizes, our work uncovers the overlooked role of ESPs in affecting the cluster configurations besides the most important metal-cage interactions. Based on this finding, we further demonstrated that one could easily regulate the internal cluster shape by changing the ESPs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"206 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144756354","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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Intrinsic polarization mechanism of CCTO based on optimized Skanavi model with displacement fields modification 基于位移场修正优化Skanavi模型的CCTO本态极化机理

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-31 DOI: 10.1039/d5cp00845j

Qin Xinrui, Pengfei Cheng, Hao 中国 Luo, kejia 中国 Geng, cuncun 中国 Kong, xin 中国 Liu, xueyan 中国 Su, Yao Heng Su, Dingze Lu

{"title":"Intrinsic polarization mechanism of CCTO based on optimized Skanavi model with displacement fields modification","authors":"Qin Xinrui, Pengfei Cheng, Hao 中国 Luo, kejia 中国 Geng, cuncun 中国 Kong, xin 中国 Liu, xueyan 中国 Su, Yao Heng Su, Dingze Lu","doi":"10.1039/d5cp00845j","DOIUrl":"https://doi.org/10.1039/d5cp00845j","url":null,"abstract":"To elucidate the microscopic origin of the giant dielectric properties in perovskite calcium copper titanate (CCTO), this study proposes a novel optimization of the Skanavi model by incorporating ionic polarization displacement fields. The optical dielectric constant is calculated using the Shannon ionic radius, which accounts for coordination number and electron spin state effects, while the static dielectric response is analyzed through the introduced displacement field. By evaluating the effective electric field ratios of Ca2+, Cu2+, Ti4+, and O2- ions under varying supercell sizes (1×1×1 to 19×19×19), we observe that Ca2+ and Ti4+ exhibit robust lattice stability, whereas Cu2+ polarization direction reverses and O2- polarization amplitude diminishes significantly. The computed optical (ε∞≈6.8) and static (εs≈77) dielectric constants align closely with sub-infrared room-temperature experimental values (ε∞=6.5, εs=70), demonstrating the model’s accuracy. Notably, in the 19×19×19 supercell, Ca2+ and TiO6 octahedra dominate the static dielectric response (contributing +61.28 and +30.81, respectively), while CuO4 squares exhibit a negative contribution (-11.94). This work provides a theoretical framework for understanding the dielectric behavior of CCTO and other high - dielectric - constant dielectrics, and offers guidance for the design of high - performance electronic materials.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"11 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747648","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

Emission of velocity correlated clusters up to Ag21+ induced by keV C60- impacting a silver surface keV C60-撞击银表面诱导速度相关团簇发射至Ag21+

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-31 DOI: 10.1039/d5cp02092a

Eran Armon, Anatoly Bekkerman, Boris Tsipinyuk, Eli Kolodney

{"title":"Emission of velocity correlated clusters up to Ag21+ induced by keV C60- impacting a silver surface","authors":"Eran Armon, Anatoly Bekkerman, Boris Tsipinyuk, Eli Kolodney","doi":"10.1039/d5cp02092a","DOIUrl":"https://doi.org/10.1039/d5cp02092a","url":null,"abstract":"Earlier measurements of the velocity correlated cluster emission ( VCCE) effect in keV C60- impact with a silver target ( Ag n+ (n=1-9) , E. Armon et al , Phys. Rev. Lett., 2014,113, 027604) are extended to much larger clusters up to Ag21+. This is the largest range of cluster size demonstrated so far for the impact induced emission of velocity correlated clusters from any target. Measurements of the kinetic energy distributions (KEDs) of all emitted Ag n+ (n=1-21) cluster ions showed that the VCCE effect as exhibited by a linear increase of most probable energies of the KEDs as a function of cluster size, E mp(n) , is still valid up to Ag21+ . The extension of the cluster size range was achieved mainly by applying a higher extraction/acceleration voltage for the surface emitted cluster ions than done before for the smaller range (Uext.= 100 V as compared with 25 V before). The preferential collection and detection of some off-normal lower energy cluster ions resulted in a rather moderate and nearly constant 1-2 eV decrease of E mp(n) as compared with the earlier (Uext..= 25 V) results. Namely, the slope of the linear E mp(n) relation (representing the strength of the VCCE effect) is nearly unaffected by the extraction voltages. It shows that the distortion of the VCCE effect by the extraction field is rather small and specifically, that the effect is getting more pronounced with decrease of the extraction voltage. The observation reported here is important for extending the range of validity of the VCCE effect and for gaining a deeper understanding of the nature and size of the (hypothesized) superhot moving precursor serving as the source for all the emitted clusters.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"26 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747622","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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Comparison of the solvation models COSMO and EC-RISM for the prediction of photoacidity in aqueous solution† 溶剂化模型COSMO与EC-RISM预测水溶液光酸度的比较

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-07-31 DOI: 10.1039/d5cp01694k

Ömer Faruk Can Tiska, Niklas Suelzner, Julia Haberhauer, Patrick Kibies, Stefan M. Kast, Christof Hattig

{"title":"Comparison of the solvation models COSMO and EC-RISM for the prediction of photoacidity in aqueous solution†","authors":"Ömer Faruk Can Tiska, Niklas Suelzner, Julia Haberhauer, Patrick Kibies, Stefan M. Kast, Christof Hattig","doi":"10.1039/d5cp01694k","DOIUrl":"https://doi.org/10.1039/d5cp01694k","url":null,"abstract":"The embedded cluster reference interaction site model (EC-RISM) and the conductor-like solvation model (COSMO) are compared in terms of their ability to predict excitation energies and photoacidity in aqueous solution. The test set includes photoacids derived from phenol, naphthol, and coumarin as well as photobases derived from quinoline. Vertical excitation energies were calculated using the approximate coupled cluster singles-and-doubles model (CC2). For the neutral and protonated forms of the photobases as well as for the neutral forms of the photoacids, EC-RISM-CC2 and COSMO-CC2 yield excitation energies that agree within approximately ±0.08 eV and are in good agreement with available experimental data. For the deprotonated forms of the photoacids, which in this study are phenolate anions throughout, COSMO significantly underestimates the effects of hydrogen bond donation in aqueous solution. In contrast, EC-RISM provides a more faithful description of these solvation effects due to its ability to model solvent distributions on an atomic level, unlike continuum approaches such as COSMO. As a result, EC-RISM performs better in predicting the photoacidity of the photoacids while yielding similar results for the photobasicity of the photobases. To approximately correct for the remaining electronic structure error of CC2, higher-order corrections were estimated from vacuum calculations with CCSDR(3) and CC3 and added to the EC-RISM-CC2 results. For the excitation energies of the photoacids, the CCSDR(3) and CC3 results exhibit significant differences, with the CC3 corrections leading to better agreement with the available experimental data in solution. However, regarding photoacidity, the estimated EC-RISM-CCSDR(3) and EC-RISM-CC3 results are very similar.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747623","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