The Journal of Physical Chemistry A最新文献_第3页

Unraveling the Anomalous Physicochemical Properties of Ethanol-Water Binary Solutions via Hydrogen-Bond-Driven Self-Assembly of Ethanol Clusters. 通过氢键驱动的乙醇簇自组装揭示乙醇-水二元溶液的异常物理化学性质。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-07-31 Epub Date: 2025-07-22 DOI: 10.1021/acs.jpca.5c03699

Yating Shang, Rahimi Hajar, Xinyue Jiang, Yuqun Xie

{"title":"Unraveling the Anomalous Physicochemical Properties of Ethanol-Water Binary Solutions via Hydrogen-Bond-Driven Self-Assembly of Ethanol Clusters.","authors":"Yating Shang, Rahimi Hajar, Xinyue Jiang, Yuqun Xie","doi":"10.1021/acs.jpca.5c03699","DOIUrl":"10.1021/acs.jpca.5c03699","url":null,"abstract":"Conventional solvents such as water and ethanol exhibit anomalous physicochemical properties in binary ethanol-water solutions, including negative relative partial molar volumes and maxima viscosity, which challenge classical equilibrium thermodynamics. While prior studies have attempted to explain these phenomena through hydrogen-bonding network behavior, experimental evidence remains insufficient. This study investigates structure characteristics of ethanol self-assembly clusters driven by hydrogen bonding, employing ethanol dehydrogenase assays, electrochemical voltammetry, electrospray ionization-mass spectrometry (ESI-MS), and micro-oxygen bomb calorimetry to verify structural features across self-assembling ethanol molecules. Results demonstrate that the distribution of electrochemically oxidizable and enzyme-accessible monomeric ethanol molecules aligns with trends in the partial molar volumes. Specifically, the anomalous inflection point at 50% ethanol concentration arises from the predominance of tetrameric ethanol clusters, as validated by ESI-MS and calorimetric data. By integration of structural chemistry principles, this work systematically elucidates the molecular origins of ethanol-water anomalies, establishing a foundational framework for theoretical interpretation.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"6837-6844"},"PeriodicalIF":2.8,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144688331","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}

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IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-07-31

Gabriele Fabbro, Jan Brandejs and Trond Saue*,

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IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-07-31

Jonas Vester*, David Carrasco-Busturia, Kenneth Ruud, Magnus Ringholm and Jógvan Magnus Haugaard Olsen*,

引用次数: 0

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-07-31

Francesca D’Ambrosio, Alice Frustaci and Enrico Bodo*,

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Preparation of Emissive Metallacycles/Cages and Their Recent Uses and Applications. 发射型金属循环/笼的制备及其最新用途与应用

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-07-31 Epub Date: 2025-06-16 DOI: 10.1021/acs.jpca.5c02128

Meilin Yu, Lingran Liu, Chongyi Chen, Xinqiong Wang, Yan Sun, Peter J Stang

引用次数: 0

Phase-Sensitive SFG of Poly(vinyl alcohol) on Calcium Fluoride: Interaction with Water Using Backside Geometry. 聚乙烯醇在氟化钙上的相敏SFG：利用背面几何与水的相互作用。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-07-31 Epub Date: 2025-07-17 DOI: 10.1021/acs.jpca.4c06453

Emma F Gubbins, Ziqing Xiong, Rebecca G Lynch, Blake Hance, Steven J Sibener, Mary Jane Shultz

{"title":"Phase-Sensitive SFG of Poly(vinyl alcohol) on Calcium Fluoride: Interaction with Water Using Backside Geometry.","authors":"Emma F Gubbins, Ziqing Xiong, Rebecca G Lynch, Blake Hance, Steven J Sibener, Mary Jane Shultz","doi":"10.1021/acs.jpca.4c06453","DOIUrl":"10.1021/acs.jpca.4c06453","url":null,"abstract":"One effective tool for probing interfaces at the atomic-molecular level, particularly buried interfaces, is nonlinear spectroscopy: sum frequency generation (SFG). SFG produces a complex response; the observed intensity is the square of this complex response. Removing complications due to the nonlinearity requires determining the complex amplitude. This contribution reports a nonlinear interferometric technique that nearly directly yields the real and imaginary components of the complex response via optical projection. Both the real and imaginary components are linear in the constituents generating the response, enabling monitoring interactions between individual moieties and added molecules. The technique is applied to poly(vinyl alcohol) (PVA) on a CaF2 substrate. PVA is of interest since it is one of the most effective synthetic ice recrystallization inhibitors (IRIs); both its configuration at the interface and its interaction with water are thought to play critical roles in its IRI activity. Results show that PVA binds in a manner reminiscent of reported simulations of PVA binding to ice; some alcohol groups strongly bind water, chemisorbing it, while other groups weakly bind water, physisorbing it. Both the polarization dependence of the SFG response and modified intensity due to the interaction with water are leveraged to assign resonances.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"6748-6758"},"PeriodicalIF":2.8,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144648010","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

Infrared Spectroscopic Study of Perfluorobenzyl Peroxyl Radical and Its UV Photolysis Products in An Argon Matrix. 全氟苯过氧自由基及其在氩气基质中紫外光解产物的红外光谱研究。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-07-31 Epub Date: 2025-07-20 DOI: 10.1021/acs.jpca.5c02095

Esfir G Baskir, Valentin D Gvozdev

{"title":"Infrared Spectroscopic Study of Perfluorobenzyl Peroxyl Radical and Its UV Photolysis Products in An Argon Matrix.","authors":"Esfir G Baskir, Valentin D Gvozdev","doi":"10.1021/acs.jpca.5c02095","DOIUrl":"10.1021/acs.jpca.5c02095","url":null,"abstract":"The perfluorobenzyl peroxyl radical (C6F5CF2O2) was prepared by the reaction of the perfluorobenzyl radical, generated in the gas phase by vacuum pyrolysis of the perfluorobenzyl iodide, with molecular oxygen. The IR spectra of the radicals C6F5CF2O2 and C6F5CF218O2 trapped in argon matrices at 10 K were measured for the first time and assigned to two conformers with the O-O moiety in anti- and gauche orientation with respect to the C-C bond by comparing the results of the matrix isolation IR spectroscopy study with the data of quantum chemical calculations at the B3LYP/aug-cc-pVTZ and CBS-QB3 levels of theory. UV photolysis of this peroxyl radical resulted in the elimination of F2C═O with the formation of the perfluorophenoxyl radical C6F5O, which formed complexes in the matrix. This reaction pathway considerably differs from that observed for the unsubstituted benzyl peroxyl radical, which decomposes to hydroxyl radical and benzaldehyde.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"6788-6797"},"PeriodicalIF":2.8,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144673369","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

Toward Validated Quantum Mechanical Workflows Predicting pH-Dependent Properties: Benchmarking Protocols for Conformational Sampling, Model Solvent, Basis Set, Density Functional, and Empirical Corrections. 预测ph相关性质的量子力学工作流程：构象采样、模型溶剂、基集、密度泛函和经验校正的基准协议。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-07-31 Epub Date: 2025-07-22 DOI: 10.1021/acs.jpca.5c01484

Donatus A Agbaglo, Minh T N Ho, Michael J Frisch, Benjamin G Janesko

{"title":"Toward Validated Quantum Mechanical Workflows Predicting pH-Dependent Properties: Benchmarking Protocols for Conformational Sampling, Model Solvent, Basis Set, Density Functional, and Empirical Corrections.","authors":"Donatus A Agbaglo, Minh T N Ho, Michael J Frisch, Benjamin G Janesko","doi":"10.1021/acs.jpca.5c01484","DOIUrl":"10.1021/acs.jpca.5c01484","url":null,"abstract":"We present work toward validated quantum-mechanical workflows predicting pH-dependent properties of flexible molecules in solution. The present contribution validates a broad set of possible workflows against a focused set of pKa data. In particular, we test two different conformational sampling protocols, four continuum solvent models, eight atomic orbital basis sets, eight density functional approximations (DFAs), two schemes for geometry optimization and incorporation of thermal effects, and three schemes for empirical correction, a total of 3076 possible approaches. We benchmark these methods' predictions for the macroscopic (experimental) pKa of 20 N-acylsulfonamides taken from the SAMPL7 challenge. Consistent with earlier studies, we find that workflows employing standard density functionals, triple-ζ basis sets, and linear empirical corrections provide root-mean-square deviations (RMSD) in pKa around 0.6-1.2 log units. Our workflows provide another step toward reliable black-box physics-based prediction of pH-dependent properties.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"6769-6779"},"PeriodicalIF":2.8,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144688330","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

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-07-31

Richard Einsele, Xincheng Miao, Luca Nils Philipp and Roland Mitrić*,

引用次数: 0

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-07-31

Paul Saxe*, Jessica Nash*, Mohammad Mostafanejad*, Eliseo Marin-Rimoldi*, Hasnain Hafiz*, Louis G. Hector Jr* and T. Daniel Crawford*,

引用次数: 0