Chemphyschem最新文献

Physical Chemistry meets Organic Chemistry: Special Issue on Physical Organic Chemistry in ChemPhysChem. 物理化学与有机化学相遇：化学物理计划中的物理有机化学特刊。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-10-17 DOI: 10.1002/cphc.202500507

Guillaume Berionni, Muriel Sebban, Jacques Maddaluno, Sami Lakhdar

引用次数: 0

Accurate Calculation of Electron Paramagnetic Resonance Parameters for Molybdenum Compounds. 钼化合物电子顺磁共振参数的精确计算。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-10-16 DOI: 10.1002/cphc.202500317

Maria Drosou, Iris Wehrung, Dimitrios A Pantazis, Maylis Orio

{"title":"Accurate Calculation of Electron Paramagnetic Resonance Parameters for Molybdenum Compounds.","authors":"Maria Drosou, Iris Wehrung, Dimitrios A Pantazis, Maylis Orio","doi":"10.1002/cphc.202500317","DOIUrl":"https://doi.org/10.1002/cphc.202500317","url":null,"abstract":"Paramagnetic molybdenum compounds are of great interest in inorganic chemistry and metalloenzyme catalysis. Electron paramagnetic resonance (EPR) spectroscopies that determine hyperfine coupling constants (HFCs) and g-tensor values are essential for investigating the electronic structure of these compounds, but require support from accurate quantum chemical approaches. Here, a database of Mo(V) complexes with well-defined structures and EPR parameters is presented, and optimal quantum chemical protocols for 95Mo HFCs and g-values are investigated. It is shown that unmodified segmented all- electron relativistically contracted (SARC) all-electron basis sets can produce converged results for HFCs and g-values with the exact-2-component (X2C) Hamiltonian. The dependence of EPR parameters on the functional is studied in detail. Double-hybrid functionals and global hybrids with high exact exchange are top performers for 95Mo HFCs, with PBE0-DH achieving the best agreement with experiment. Comparison of density functional theory (DFT)-derived HFCs with values obtained by coupled cluster theory with the domain-based local pair natural orbital approach (DLPNO-CCSD) shows that DFT remains the method of choice for the present set of compounds. Smaller differentiation among functionals is observed for g-tensors, although PBE0-DH is still a top performer and can be recommended as the most reliable approach overall for describing both valence and core properties of Mo compounds.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500317"},"PeriodicalIF":2.2,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145307016","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

Different Reactions Define the Electrochemical Window in 1-Butyl-3-Methylimidazolium Triflate on Gold and Platinum Electrodes. 3-甲基咪唑在金、铂电极上的电化学窗口。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-10-16 DOI: 10.1002/cphc.202500096

Frederik J Stender, Marcel Risch

{"title":"Different Reactions Define the Electrochemical Window in 1-Butyl-3-Methylimidazolium Triflate on Gold and Platinum Electrodes.","authors":"Frederik J Stender, Marcel Risch","doi":"10.1002/cphc.202500096","DOIUrl":"https://doi.org/10.1002/cphc.202500096","url":null,"abstract":"Ionic liquids (IL) make excellent candidates for many energy storage devices due to unique and tunable properties such as a large electrochemical window (ECW). Water as an impurity in 1-butyl-3-methylimidazolium (BMIM) triflate is investigated on platinum and gold electrodes in a stagnant glass cell and in a flow-cell coupled to a differential electrochemical mass spectrometer (DEMS). It is found that the ECW closes with increasing water content on both gold and platinum electrodes in both setups. Platinum has a smaller ECW than gold, where the difference mainly stems from the limiting reduction reaction, as identified based on DEMS. Below 1.11 MH2O/LIL, the anodic reaction is predominantly IL decomposition and above the oxygen evolution reaction for both materials. The cathodic limit is given by the hydrogen evolution reaction for platinum independent of water content and gold above 1.66 MH2O/LIL, while it is IL decomposition below. The study highlights the interplay between electrode material and electrolyte for tailoring the ECW for applications involving intentional or unintentional mixing of water with IL.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500096"},"PeriodicalIF":2.2,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306976","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

Resonance Response to Intermolecular Interaction: A Natural Resonance Theory Analysis. 分子间相互作用的共振响应：自然共振理论分析。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-10-16 DOI: 10.1002/cphc.202500352

Jakub Brzeski

{"title":"Resonance Response to Intermolecular Interaction: A Natural Resonance Theory Analysis.","authors":"Jakub Brzeski","doi":"10.1002/cphc.202500352","DOIUrl":"https://doi.org/10.1002/cphc.202500352","url":null,"abstract":"Although the concept of resonance is a key element of any organic chemistry course, its modulation by supramolecular stabilization remains poorly explored. This article seeks to address this issue with the use of natural resonance theory and other computational tools such as ab initio methods (DF-MP2, coupled-cluster singles and doubles, and SAPT2 + 3(CCD)δMP2), interaction region indicator, and charge-transfer analysis. A set of structurally straightforward noncovalently bonded systems with general formula X/H2O where X = CO2, SO2, HCONH2, C4H4O, and C6H5NH2 is subjected to investigation. The findings indicate that the complexation can have significant impact on the relative weights of the resonance structures observed for isolated X by up to 32%. Furthermore, formation of X/H2O complex is found to introduce new resonance structures with water's outer-valence electrons participating in the resonance. These findings broaden understanding of how supramolecular interactions shape resonance, a fundamental concept in chemistry, and can improve predictions of molecular behavior in complex systems.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500352"},"PeriodicalIF":2.2,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306960","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 Paddlewheels Impact the Dynamics of Superionic Conduction in AgI. 电子桨轮对AgI中超离子传导动力学的影响。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-10-16 DOI: 10.1002/cphc.202500077

Harender S Dhattarwal, Richard C Remsing

{"title":"Electronic Paddlewheels Impact the Dynamics of Superionic Conduction in AgI.","authors":"Harender S Dhattarwal, Richard C Remsing","doi":"10.1002/cphc.202500077","DOIUrl":"https://doi.org/10.1002/cphc.202500077","url":null,"abstract":"Solid-state ion conductors hold promise as next-generation battery materials. To realize their full potential, an understanding of atomic-scale ion conduction mechanisms is needed, including ionic and electronic degrees of freedom. Molecular simulations can create such an understanding; however, including a description of electronic structure necessitates computationally expensive methods that limit their application to small scales. We examine an alternative approach in which neural network models are used to efficiently sample ionic configurations and dynamics at ab initio accuracy. Then, these configurations are used to determine electronic properties in a postprocessing step. We demonstrate this approach by modeling the superionic phase of AgI, in which cation diffusion is coupled to rotational motion of local electron density on the surrounding iodide ions, termed electronic paddlewheels. The neural network potential can capture the many-body effects of electronic paddlewheels on ionic dynamics, but classical force field models cannot. Through an analysis rooted in the generalized Langevin equation framework, we find that electronic paddlewheels have a significant impact on the time-dependent friction experienced by a mobile cation. Our approach will enable investigations of electronic fluctuations in materials on large length and time scales, and ultimately the control of ion dynamics through electronic paddlewheels.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500077"},"PeriodicalIF":2.2,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145307025","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

Toward a Generalizable Prediction Model of Molten Salt Mixture Density with Chemistry-Informed Transfer Learning. 基于化学信息迁移学习的熔盐混合物密度可推广预测模型。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-10-14 DOI: 10.1002/cphc.202500273

Julian Barra, Shayan Shahbazi, Anthony Birri, Rajni Chahal, Ibrahim Isah, Muhammad Nouman Anwar, Tyler Starkus, Prasanna Balaprakash, Stephen Lam

{"title":"Toward a Generalizable Prediction Model of Molten Salt Mixture Density with Chemistry-Informed Transfer Learning.","authors":"Julian Barra, Shayan Shahbazi, Anthony Birri, Rajni Chahal, Ibrahim Isah, Muhammad Nouman Anwar, Tyler Starkus, Prasanna Balaprakash, Stephen Lam","doi":"10.1002/cphc.202500273","DOIUrl":"https://doi.org/10.1002/cphc.202500273","url":null,"abstract":"Optimally designing applications of molten salts requires knowledge of their thermophysical properties over a wide range of temperatures and compositions. There exist significant gaps in existing databases and this data can be challenging to experimentally measure due to high temperatures, salt corrosivity, and salt hygroscopicity. Existing databases have been used to create Redlich-Kister (RK) models for mixture density showing improved accuracy with respect to ideal mixing assumptions, but these models require subcomponent data measurements for each new system, therefore lacking generality. In order to address generalizability and data sparsity, a transfer learning procedure is proposed to train deep neural networks (DNNs) using a combination of semi-empirical relationships (RK), data from the thermophysical arm of the molten salt thermal properties database and universal ab initio properties of component mixtures taken from the joint automated repository for various integrated simulations (JARVIS) classical force-field inspired descriptors database to predict density in molten salts. Herein, it is shown that DNNs predict molten salt density with an r2 over 0.99 and a mean absolute percentage error under 1%, outperforming alternative methods.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500273"},"PeriodicalIF":2.2,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145291406","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

Cooperative Halogen Bonding and π-π Stacking Interactions as Drivers of Polymorphism. 协同卤素键和π-π堆叠相互作用是多态性的驱动因素。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-10-14 DOI: 10.1002/cphc.202500491

Marcin S Małecki, Marcin Moskwa, Przemysław Dopieralski, Sławomir Szafert

引用次数: 0

Rapid and Reliable Conformational Analysis of Glycans by Small Angle X-Ray Scattering Guided Molecular Dynamics Simulations. 小角x射线散射引导分子动力学模拟快速可靠的聚糖构象分析。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-10-14 DOI: 10.1002/cphc.202500323

Yadiel Vázquez-Mena, Nishu Yadav, Surusch Djalali, Isabelle Morfin, Martina Delbianco, Yu Ogawa

{"title":"Rapid and Reliable Conformational Analysis of Glycans by Small Angle X-Ray Scattering Guided Molecular Dynamics Simulations.","authors":"Yadiel Vázquez-Mena, Nishu Yadav, Surusch Djalali, Isabelle Morfin, Martina Delbianco, Yu Ogawa","doi":"10.1002/cphc.202500323","DOIUrl":"https://doi.org/10.1002/cphc.202500323","url":null,"abstract":"Glycan conformations play essential roles in biological recognition, immune response, and cellular communication, as well as the properties of carbohydrate-based materials. Despite their importance, analyzing their secondary structures poses significant challenges due to their inherent molecular flexibility and extensive hydration. Traditional techniques like nuclear magnetic resonance (NMR) and X-ray crystallography often struggle to capture their dynamic nature accurately. Computational approaches, particularly molecular dynamics (MD) simulations, have emerged as a powerful tool to study glycan conformations, but their accuracy relies heavily on validation against experimental data. In this study, the conformation of glycans in the solution state is investigated by integrating small-angle X-ray scattering (SAXS) and MD simulations. By explicitly accounting for the conformational dynamics and hydration effects, the MD simulations accurately predicted the SAXS intensities of two glycan hairpins with similar primary sequences. This approach enables the resolving of their intricate conformational properties, including distinct secondary structures, radii of gyration, and conformational rigidity and dynamics. These findings offer a robust, label-free analytical strategy for glycan conformational studies, with potential applications in the molecular design of glycan-based materials and therapeutics.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500323"},"PeriodicalIF":2.2,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145291385","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

Spontaneous Mirror-Symmetry Breaking Destabilizes Racemates: A Route to Homochirality and Reversed Chemical Selectivity. 自发镜像对称破缺使外消旋物失稳：一条通向同手性和逆转化学选择性的途径。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-10-10 DOI: 10.1002/cphc.202500384

Josep M Ribó, Jean-Claude Micheau, Thomas Buhse

引用次数: 0

Difluorinated Cyclohexanes: Energetics and Intra- and Intermolecular Interactions. 二氟化环己烷：能量学和分子内与分子间相互作用。

IF 2.2 3区化学

Chemphyschem Pub Date : 2025-10-10 DOI: 10.1002/cphc.202500648

Matheus P Freitas

引用次数: 0