The Journal of Physical Chemistry A最新文献_第8页

Modeling Pb(II) Adsorption on Mineral Surfaces: Bridging Density Functional Theory and Experiment with Thermodynamic Insights

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-03-06 DOI: 10.1021/acs.jpca.5c0039010.1021/acs.jpca.5c00390

Jennifer L. Bjorklund, Logan J. Augustine, Ali Abbaspour Tamijani, Thomas P. Trainor, Anne M. Chaka and Sara E. Mason*,

{"title":"Modeling Pb(II) Adsorption on Mineral Surfaces: Bridging Density Functional Theory and Experiment with Thermodynamic Insights","authors":"Jennifer L. Bjorklund, Logan J. Augustine, Ali Abbaspour Tamijani, Thomas P. Trainor, Anne M. Chaka and Sara E. Mason*, ","doi":"10.1021/acs.jpca.5c0039010.1021/acs.jpca.5c00390","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00390https://doi.org/10.1021/acs.jpca.5c00390","url":null,"abstract":"Despite decades of work on aqueous lead (Pb) adsorption on α-Fe2O3 (hematite) and α-Al2O3 (alumina), gaps between measurements and modeling obscure molecular-level understanding. Achieving well-matched geometries between theory and experiment for mineral-water interfaces is a hurdle, as surface functional group type and distribution must be accounted for in determining mechanisms. Additionally, computational methods that can describe the substrate are often not appropriate to capture aqueous effects. Progress requires focusing on well-studied and relevant systems, such as key facets (001), (012), and (110) of hematite and alumina, and ubiquitous contaminants such as aqueous Pb. In the past, bulk-parameterized bond-valence principles were used to rationalize Pb(II) adsorption trends. These approaches can break down at surfaces, where flexible bonding environments and adsorption-induced surface relaxations play a critical role. Here, we adapt and apply a density functional theory (DFT) and thermodynamics framework, integrating DFT-calculated energies with experimental data and electrochemical principles, to predict Pb(II) adsorption. Our model results capture trends across the full set of surfaces and predict that inner-sphere Pb(II) sorption on (001) alumina varies from unfavorable to weakly favorable across a range of pH conditions. This aligns with experimental insights that Pb(II) interacts at that surface through outer-sphere interactions. Extending to Fe(II) adsorption, we demonstrate a coverage-dependent site preference, potentially explaining disorder in overlayers grown by the oxidative adsorption of Fe(II) on hematite (001).","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 11","pages":"2754–2767 2754–2767"},"PeriodicalIF":2.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Imaging the Photochemistry of the Hydrogen-Bonded Heptazine-Water Complex with Femtosecond Time-Resolved Spectroscopy: A Computational Study.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-03-06 Epub Date: 2025-02-20 DOI: 10.1021/acs.jpca.4c08085

Sebastian V Pios, Maxim F Gelin, Wolfgang Domcke, Lipeng Chen

{"title":"Imaging the Photochemistry of the Hydrogen-Bonded Heptazine-Water Complex with Femtosecond Time-Resolved Spectroscopy: A Computational Study.","authors":"Sebastian V Pios, Maxim F Gelin, Wolfgang Domcke, Lipeng Chen","doi":"10.1021/acs.jpca.4c08085","DOIUrl":"10.1021/acs.jpca.4c08085","url":null,"abstract":"Graphitic carbon nitride (g-CN) has attracted vast interest as a promising inexpensive metal-free photocatalyst for water splitting with solar photons. The heptazine (Hz) molecule is the building block of graphitic carbon nitride. The photochemistry of the Hz molecule and derivatives thereof in protic environments has been the subject of several recent experimental and computational studies. In the present work, the hydrogen-bonded Hz···H2O complex was adopted as a model system for the exploration of photoinduced electron and proton transfer processes in this complex with quasi-classical nonadiabatic trajectory simulations, using the ab initio ADC(2) electronic-structure method and a computationally efficient surface-hopping algorithm. The population of the optically excited bright 1ππ* state of the Hz chromophore relaxes through three 1nπ* states and a low-lying charge-transfer state, which drives proton transfer from H2O to Hz, to the long-lived optically dark S1(ππ*) state of Hz. The imaging of this ultrafast and complex dynamics with femtosecond time-resolved transient absorption (TA) pump-probe (PP) spectroscopy and two-dimensional (2D) electronic spectroscopy (ES) was computationally explored in the framework of the quasi-classical doorway-window approximation. By comparison of the spectra of the Hz···H2O complex with those of the free Hz molecule, the effects of the hydrogen bond on the ultrafast internal conversion dynamics can be identified in the spectroscopic signals. Albeit the TA PP and 2D ES spectroscopies are primarily sensitive to electronic excited-state dynamics and less so to proton transfer dynamics, they nevertheless can provide mechanistic insights which can contribute to the acceleration of the optimization of photocatalysts for water splitting.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"2217-2226"},"PeriodicalIF":2.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143466576","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Quantitative Kinetics of the Hydrogen Shift Reaction of Methylthiomethyl Peroxy Radical (CH₃SCH₂OO) in the Atmosphere.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-03-06 Epub Date: 2025-02-23 DOI: 10.1021/acs.jpca.4c06818

Yu Xia, Weijun Zhang, Xiaofeng Tang, Bo Long

{"title":"Quantitative Kinetics of the Hydrogen Shift Reaction of Methylthiomethyl Peroxy Radical (CH3SCH2OO) in the Atmosphere.","authors":"Yu Xia, Weijun Zhang, Xiaofeng Tang, Bo Long","doi":"10.1021/acs.jpca.4c06818","DOIUrl":"10.1021/acs.jpca.4c06818","url":null,"abstract":"Hydrogen shift processes of peroxy radicals are paramount to understanding atmospheric chemical oxidations of volatile organic compounds. However, quantifying these processes using experimental and theoretical methods is also very difficult. Here, we chose methylthiomethyl peroxy radical (CH3SCH2OO) as a typical reaction to investigate the hydrogen shift in CH3SCH2OO using a dual-level (DL) strategy. In the DL strategy, GMMQ.L3//CCSD(T)-F12a/cc-pVTZ-F12 is used as a high-level method to calculate the rate constant using transition state theory. Here, GMMQ.L3 is a newly developed composite method for single-point energy calculations that approximates CCSDTQ/CBS accuracy (coupled cluster theory with single, double, triple, and connected quadruple excitations at the complete basis set limit). Additionally, MN15/MG3S is used as a low level to do multistructural canonical variational transition state theory with large curvature tunneling (MS-CVT/LCT) calculations. The calculated rate constants of 0.05-0.08 s-1 agree well with the corresponding experimental values and the previous MC-TST results for the hydrogen shift of CH3SCH2OO at 293-298 K. The calculated results unravel that the zero-point vibrational energies depend strongly on the basis set in the CCSD(T)-F12 calculations. We find the large effects of the enthalpy of activation at 0 K, tunneling, and multistructural torsional anharmonicity on the calculated rate constant of the hydrogen shift of CH3SCH2OO. The current study provides a valuable reference case for the quantitative kinetic calculations of the peroxy radical isomerization reaction in the atmosphere.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"2275-2285"},"PeriodicalIF":2.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143481738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Crystalline Organic Compounds as Effective Nuclei in Contact Efflorescence of Ammonium Sulfate.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-03-06 Epub Date: 2025-02-25 DOI: 10.1021/acs.jpca.4c07566

Kyle A McMillan, Ryan D Davis, Margaret A Tolbert

{"title":"Crystalline Organic Compounds as Effective Nuclei in Contact Efflorescence of Ammonium Sulfate.","authors":"Kyle A McMillan, Ryan D Davis, Margaret A Tolbert","doi":"10.1021/acs.jpca.4c07566","DOIUrl":"10.1021/acs.jpca.4c07566","url":null,"abstract":"Contact nucleation is believed to play a role in liquid-to-solid phase transitions in the atmosphere including ice nucleation and salt efflorescence. Here contact efflorescence of optically levitated ammonium sulfate droplets by collisions with organic particles is probed using a long working-distance optical trap. Two highly viscous water-soluble organic compounds (d-(+)-raffinose and citric acid), and two insoluble highly surface-active organic compounds (stearic acid and cis-pinonic acid) were probed for their ability to induce efflorescence upon contact. While three of the organics showed minimal effectiveness as contact nuclei, cis-pinonic acid showed a remarkable ability to initiate contact efflorescence of ammonium sulfate, occurring near ammonium sulfate's deliquescence relative humidity. Further analysis of cis-pinonic acid using bright-field microscopy in an electrodynamic balance provided evidence that the cis-pinonic acid particles are crystalline under the laboratory conditions. We suggest that the close lattice match between crystalline ammonium sulfate and crystalline cis-pinonic acid may account for the observed effectiveness in initiating contact efflorescence of ammonium sulfate. In contrast, tests of contact nucleation between cis-pinonic acid and sodium chloride, a pair with a poor lattice match, did not result in efflorescence. These findings suggest that crystalline organic compounds in the atmosphere could act as effective nuclei for contact efflorescence of atmospherically relevant salts, provided they share a compatible lattice structure.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"2296-2307"},"PeriodicalIF":2.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143490335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Accelerating Global Optimization of Cerium Oxide Nanocluster Structures with High-Dimensional Neural Network Potential.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-03-06 Epub Date: 2025-02-25 DOI: 10.1021/acs.jpca.4c07840

Jinyuan Shi, Qinghua Ren, Yi Gao

{"title":"Accelerating Global Optimization of Cerium Oxide Nanocluster Structures with High-Dimensional Neural Network Potential.","authors":"Jinyuan Shi, Qinghua Ren, Yi Gao","doi":"10.1021/acs.jpca.4c07840","DOIUrl":"10.1021/acs.jpca.4c07840","url":null,"abstract":"CeO2, characterized by its unique 4f electronic structure and high oxygen storage capacity, is widely recognized as an important catalyst and support material in energy and catalytic applications. Despite its importance, the complexity of CeO2 nanoclusters poses challenges for structural characterization. Herein, we present a machine learning approach to accelerate the global optimization of cerium oxide nanocluster structures using a high-dimensional neural network potential (HDNNP). Our methodology integrates active learning to construct a versatile HDNNP that enables the exploration of the vast configurational space of small to medium cerium oxide clusters (CenO2n+x, n = 2-18, x = -1, 0, +1). The HDNNP, refined through iterative active learning, achieves an accuracy comparable to first-principles calculations. Results indicate that the configuration of the lowest energy structures varies across different intervals. At n = 9 and n = 14, there is a transition from compact structures to multilayered ordered structures, and subsequently to pyramidal structures. When n > 14, almost all structures are derived from the pyramidal structure as the core grows continuously. In addition, the electronic structures of the lowest-energy clusters are analyzed. Our findings provide insights into the size-dependent stability and electronic behavior of cerium oxide nanoclusters.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"2190-2199"},"PeriodicalIF":2.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143497557","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Continuous Evolution of Eu²⁺/Eu³⁺ Mixed Valency Driven by Pressure and Temperature. 由压力和温度驱动的 Eu2+/Eu3+ 混合价的连续演化。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-03-06 Epub Date: 2025-02-25 DOI: 10.1021/acs.jpca.4c08660

Mingyu Xu, Greeshma C Jose, Mouyang Cheng, Cheng Peng, Jose L Gonzalez Jimenez, Wenli Bi, Mingda Li, Weiwei Xie

引用次数: 0

Modeling Pb(II) Adsorption on Mineral Surfaces: Bridging Density Functional Theory and Experiment with Thermodynamic Insights.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-03-06 DOI: 10.1021/acs.jpca.5c00390

Jennifer L Bjorklund, Logan J Augustine, Ali Abbaspour Tamijani, Thomas P Trainor, Anne M Chaka, Sara E Mason

{"title":"Modeling Pb(II) Adsorption on Mineral Surfaces: Bridging Density Functional Theory and Experiment with Thermodynamic Insights.","authors":"Jennifer L Bjorklund, Logan J Augustine, Ali Abbaspour Tamijani, Thomas P Trainor, Anne M Chaka, Sara E Mason","doi":"10.1021/acs.jpca.5c00390","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00390","url":null,"abstract":"Despite decades of work on aqueous lead (Pb) adsorption on α-Fe2O3 (hematite) and α-Al2O3 (alumina), gaps between measurements and modeling obscure molecular-level understanding. Achieving well-matched geometries between theory and experiment for mineral-water interfaces is a hurdle, as surface functional group type and distribution must be accounted for in determining mechanisms. Additionally, computational methods that can describe the substrate are often not appropriate to capture aqueous effects. Progress requires focusing on well-studied and relevant systems, such as key facets (001), (012), and (110) of hematite and alumina, and ubiquitous contaminants such as aqueous Pb. In the past, bulk-parameterized bond-valence principles were used to rationalize Pb(II) adsorption trends. These approaches can break down at surfaces, where flexible bonding environments and adsorption-induced surface relaxations play a critical role. Here, we adapt and apply a density functional theory (DFT) and thermodynamics framework, integrating DFT-calculated energies with experimental data and electrochemical principles, to predict Pb(II) adsorption. Our model results capture trends across the full set of surfaces and predict that inner-sphere Pb(II) sorption on (001) alumina varies from unfavorable to weakly favorable across a range of pH conditions. This aligns with experimental insights that Pb(II) interacts at that surface through outer-sphere interactions. Extending to Fe(II) adsorption, we demonstrate a coverage-dependent site preference, potentially explaining disorder in overlayers grown by the oxidative adsorption of Fe(II) on hematite (001).","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143571567","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Quantum-Electrodynamical Density-Functional Theory Exemplified by the Quantum Rabi Model.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-03-06 Epub Date: 2025-02-19 DOI: 10.1021/acs.jpca.4c07690

Vebjørn H Bakkestuen, Vegard Falmår, Maryam Lotfigolian, Markus Penz, Michael Ruggenthaler, Andre Laestadius

引用次数: 0

Importance of Charge Balance for the Embedding of Zwitterionic Solutes in the Fragment Molecular Orbital Method. 片段分子轨道法中电荷平衡对两性离子溶质包埋的重要性。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-03-06 Epub Date: 2024-12-12 DOI: 10.1021/acs.jpca.4c07218

Dmitri G Fedorov

引用次数: 0

Nonlinear Optics Materials Designed by Intramolecular Boron- and Nitrogen-Locking Strategies: Exploring Torsion Angle Descriptors.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-03-06 Epub Date: 2025-02-19 DOI: 10.1021/acs.jpca.4c07831

Bo Li, Shichen Lin, Feng Long Gu

{"title":"Nonlinear Optics Materials Designed by Intramolecular Boron- and Nitrogen-Locking Strategies: Exploring Torsion Angle Descriptors.","authors":"Bo Li, Shichen Lin, Feng Long Gu","doi":"10.1021/acs.jpca.4c07831","DOIUrl":"10.1021/acs.jpca.4c07831","url":null,"abstract":"Gaining mechanistic insights into the structure-performance relationship connecting the donor and acceptor is essential to the rational design of high performance nonlinear optics (NLO) materials. Here, intramolecular boron/nitrogen (B/N)-locking strategies in combination with various electron-withdrawing groups, R (R = TXO, DPzS, TTR, DPyS, DTC, DSCZ, DMPS and TXO2), are proposed to address this issue. With the decreasing of torsion angles (θ1 and θ2) between donor (TPA) and acceptor (Py-Ph) units, the first hyperpolarizability (β) values are increased 45-65% and 4-27% by intramolecular B/N-locking strategies, respectively. Intriguingly, we also found some good linear correlations between θ1, θ2, and lgβ (where the determination coefficient R2 ranges from 0.84 to 1.00). Meanwhile, between θ1, θ2, and the excited energy (ΔE) of the crucial excited state there have also good correlations, namely, the R2 ranges from 0.80 to 1.00. As a result, given the fact of finding results, one can draw some meaningful insights, namely, intramolecular B/N-locking strategies hold good application perspective for enhancing β, and θ1 and θ2 can serve as effective descriptors in designing high-performance NLO materials based on the D-A architecture system.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"2182-2189"},"PeriodicalIF":2.7,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447497","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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