ChemphyschemPub Date : 2025-10-17DOI: 10.1002/cphc.202500507
Guillaume Berionni, Muriel Sebban, Jacques Maddaluno, Sami Lakhdar
{"title":"Physical Chemistry meets Organic Chemistry: Special Issue on Physical Organic Chemistry in ChemPhysChem.","authors":"Guillaume Berionni, Muriel Sebban, Jacques Maddaluno, Sami Lakhdar","doi":"10.1002/cphc.202500507","DOIUrl":"https://doi.org/10.1002/cphc.202500507","url":null,"abstract":"<p><p>Professor François Terrier, Emeritus Professor of the University of Versailles Saint-Quentin, Versailles, France, passed away in July 2024. He was a key figure in physical organic chemistry and a pioneer in this field in Europe. The breadth of Prof. Terrier's contribution to science was remarkable. His former collaborators and colleagues and researchers involved in the field of physical organic chemistry are gathering with ChemPhysChem to commemorate Prof. Terrier's contributions in the form of a special issue devoted to physical organic chemistry.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2500507"},"PeriodicalIF":2.2,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145307019","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}
ChemphyschemPub Date : 2025-10-16DOI: 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":"<p><p>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 <sup>95</sup>Mo 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 <sup>95</sup>Mo 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.</p>","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}
ChemphyschemPub Date : 2025-10-16DOI: 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":"<p><p>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 M<sub>H2O</sub>/L<sub>IL</sub>, 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 M<sub>H2O</sub>/L<sub>IL</sub>, 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.</p>","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}
ChemphyschemPub Date : 2025-10-16DOI: 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":"<p><p>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)δ<sub>MP2</sub>), interaction region indicator, and charge-transfer analysis. A set of structurally straightforward noncovalently bonded systems with general formula X/H<sub>2</sub>O where X = CO<sub>2</sub>, SO<sub>2</sub>, HCONH<sub>2</sub>, C<sub>4</sub>H<sub>4</sub>O, and C<sub>6</sub>H<sub>5</sub>NH<sub>2</sub> 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/H<sub>2</sub>O 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.</p>","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}
ChemphyschemPub Date : 2025-10-16DOI: 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":"<p><p>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.</p>","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}
ChemphyschemPub Date : 2025-10-14DOI: 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":"<p><p>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 r<sup>2</sup> over 0.99 and a mean absolute percentage error under 1%, outperforming alternative methods.</p>","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}
ChemphyschemPub Date : 2025-10-14DOI: 10.1002/cphc.202500491
Marcin S Małecki, Marcin Moskwa, Przemysław Dopieralski, Sławomir Szafert
{"title":"Cooperative Halogen Bonding and π-π Stacking Interactions as Drivers of Polymorphism.","authors":"Marcin S Małecki, Marcin Moskwa, Przemysław Dopieralski, Sławomir Szafert","doi":"10.1002/cphc.202500491","DOIUrl":"https://doi.org/10.1002/cphc.202500491","url":null,"abstract":"<p><p>Understanding the mechanisms underlying the formation of different polymorphic forms of a given compound is a fundamental issue in modern physical chemistry, with significant implications for the design of functional materials, including those with pharmaceutical relevance. In the present study, the formation of two polymorphic forms of a polyyne compound is elucidated, as confirmed by X-ray crystallographic analysis. The emergence of these polymorphs results from a delicate interplay between halogen bonding and a network of noncovalent π-π stacking interactions. A combination of experimental techniques, single-crystal X-ray diffraction, and theoretical studies allows us to construct a coherent model that rationalizes the formation of both polymorphic modifications of the investigated system.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500491"},"PeriodicalIF":2.2,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145291371","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}
{"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":"<p><p>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.</p>","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}
ChemphyschemPub Date : 2025-10-10DOI: 10.1002/cphc.202500384
Josep M Ribó, Jean-Claude Micheau, Thomas Buhse
{"title":"Spontaneous Mirror-Symmetry Breaking Destabilizes Racemates: A Route to Homochirality and Reversed Chemical Selectivity.","authors":"Josep M Ribó, Jean-Claude Micheau, Thomas Buhse","doi":"10.1002/cphc.202500384","DOIUrl":"https://doi.org/10.1002/cphc.202500384","url":null,"abstract":"<p><p>Several models and experiments yielding to spontaneous mirror-symmetry breaking (SMSB) have been revisited. It is concluded that all show first-order autocatalytic dynamics for the emergence of an enantiomeric excesses (ee). However, first-order autocatalysis is by itself unable to lead to SMSB. Therefore, the emergence of scalemic nonequilibrium stationary state (NESS) is due to racemate destabilization through the coupling of autocatalysis with other enantioselective reactions. In contrast with the nonlinear effects and kinetic control in asymmetric synthesis SMSB appears as the signature of a bifurcation scenario leading to scalemic NESSs. Stoichiometric network analysis points to the potential interest of these autocatalytic networks to interpret the changes in the chemical selectivity between nonenantiomeric competitive replicators in far-from-equilibrium conditions.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500384"},"PeriodicalIF":2.2,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145257586","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}
ChemphyschemPub Date : 2025-10-10DOI: 10.1002/cphc.202500648
Matheus P Freitas
{"title":"Difluorinated Cyclohexanes: Energetics and Intra- and Intermolecular Interactions.","authors":"Matheus P Freitas","doi":"10.1002/cphc.202500648","DOIUrl":"https://doi.org/10.1002/cphc.202500648","url":null,"abstract":"<p><p>Fluorinated cyclohexanes are essential building blocks for high-performance molecules, including ion carriers and liquid crystals. This quantum-chemical study evaluates the relative energies of all difluorinated cyclohexane isomers, highlighting key intramolecular interactions as thermodynamic modulators. The stability of 1,1-difluorocyclohexane arises from an anomeric-like n<sub>F</sub> → σ*<sub>CF</sub> interaction, despite FCF repulsion. Dipolar repulsion between CF bonds affects isomers like diequatorial trans-1,2 and diaxial cis-1,3, while axial CH···CF electrostatic attraction stabilizes trans-1,3 and diaxial trans-1,4 isomers. Hyperconjugation involving antiperiplanar CH and CF bonds also contributes. Notably, diaxial CF bonds facilitate self-assembly via interactions between negatively charged fluorines and positively charged hydrogens. This study advances understanding of fluorinated cyclohexanes' thermodynamic behavior, providing a framework for designing tailored fluorinated compounds for advanced applications.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500648"},"PeriodicalIF":2.2,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145274083","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}