Physical Chemistry Chemical Physics

doi: 10.1039/d5cp90199epmid: N/A

doi: 10.1039/d5cp90200bpmid: N/A

doi: 10.1039/d5cp90201kpmid: N/A

Elgayyar, Taha; Azzolina-Jury, Federico; Thibault-Starzyk, Frédéric

doi: 10.1039/d5cp02197apmid: 41114729

IR spectroscopy has been extensively employed to characterize the structural and vibrational properties of carbonates; yet, its application in studying the adsorption capacity of carbonate surfaces remains limited. This short review presents the use of FTIR as a powerful tool for investigating the structure and surface chemistry of carbonates, which is relevant to several environmental and industrial applications (such as CO2 capture and storage). Several FTIR techniques provide detailed analysis of the structure of carbonate polymorphs (calcite, aragonite, vaterite, and amorphous phases) alongside their phase transformation kinetics. In addition, adsorption studies of various molecules (CO, CO2, H2O, acids and several HCs) were performed to identify the adsorption sites, mechanisms and intermediates. These insights highlight the significance of IR spectroscopy for understanding the carbonate structure and surface properties, and guide future research in several environmental and industrial processes where carbonates are involved.

Murray, Jane S.

doi: 10.1039/d5cp03714jpmid: 41111281

This short survey involving fluorine as an atom and as a partner in molecules/ions and its applicability to many fields begins with its discovery by Henri Moissan in 1886, for which the discoverer received the Nobel Prize in 1906, short before his death. Fluorine has an anomalous nature that plays a role in all its interactions. This will be discussed in detail. Perfluorination, as introduced by DuPont and others and then by the Resnati group, will then be discussed. This led to the recognition of myriads of noncovalent interactions, involving not only the larger halogens but other columns of the periodic table. Recent applications of the use of fluorine as a substituent will be discussed.

Zhou, Zichun; Zhang, Han; Song, Chi; Ming, Chen; Sun, Yi-Yang

doi: 10.1039/d5cp03582apmid: 41111395

Large language models have been extensively employed for scientific research from different aspects, yet their performance is often limited by gaps in highly specialized knowledge. To bridge this divide, in this perspective we take phosphor materials for white LED applications as a model system and construct a domain-specific knowledge base that couples retrieval-augmented generation with a numerical-querying model context protocol. By automatically extracting and structuring data from more than 5400 publications—including chemical compositions, crystallographic parameters, excitation-emission wavelengths, and synthesis conditions—we construct an artificial-intelligence agent that delivers both broad semantic search and exact parameter lookup, each answer accompanied by verifiable references. This hybrid approach mitigates hallucinations, and improves recall and precision in expert-level question-answering. Finally, we outline how linking this curated corpus to lightweight machine-learning models and even automated experimental synthesis facilities can close the loop from target specification to experimental validation, offering a blueprint for accelerated materials discovery.

Bartha, Cristina; Locovei, Claudiu; Alexandru-Dinu, Andrei; Comanescu, Cezar; Grigoroscuta, Mihai Alexandru; Kuncser, Andrei; Iacob, Nicusor; Galatanu, Magda; Leca, Aurel; Badica, Petre; Kuncser, Victor

doi: 10.1039/d5cp02696bpmid: 41099085

The precise control of the magnetic compensation temperature (θc) in ferrimagnetic garnets is essential for the development of cutting-edge ultrafast customizable spintronic devices. In this work we demonstrate how fine variation in stoichiometry and cation distribution in iron gadolinium garnets significanty influences θc. Two samples of Gd3Fe5O112 garnets synthesized via a new hydrothermal method and a conventional solid-state reaction, respectively, were considered. The complex study was carried out using a complex approach combining X-ray diffraction, magnetometry, and Mössbauer spectroscopy. Atomic-scale analysis revealed with unprecedent accuracy a cationic inversion between Fe3+ ang Gd3+ at octahedral and dodecahedral sites in both samples, and their chemical compositions were determined as Gd2.70Fe4.76O11.9 and Gd2.96Fe4.68O11.5, respectively. These local rearrangements have been shown to have a consistent influence on θc (290 K and 317 K, respectively) around room temperature, emphasizing the high sensitivity of exchange interactions to internal atomic order. Results clearly illustrate the strong correlation between the processing, atomic configuration and macroscopic magnetic behavior, establishing a new paradigm for the design of garnet-based materials with tunable θc. The strategy for the accurate determination of cation inversion illustrated in this work exhibits great potential in guiding material innovations for next-generation spintronics.

Ishraaq, Raashiq; Das, Siddhartha

doi: 10.1039/d5cp02528apmid: 41099796

In this communication, we employ a combination of all-atom molecular dynamics simulations and machine learning to establish the effect of different halide screening counterions (fluoride, chloride, bromide, and iodide ions) on the prevalence of two separate hydration states of the {N(CH3)3}+ functional group of the PMETA (([poly(2-(methacryloyloxy)ethyl) trimethylammonium) cationic brushes.

Yadav, Shilpa; Lee, JuHyeon; Meijer, Gerard; Eibenberger-Arias, Sandra

doi: 10.1039/d5cp02854jpmid: 41036549

The rotationally resolved excitation spectrum of the S1 ← S0 electronic transition of the chiral molecule 1-phenylethanol is measured via laser-induced fluorescence detection in a cold, seeded molecular beam. The rotational constants and structure of the S1 state are determined by fitting 419 spectral lines. The transition dipole moment is found to have predominant projections along the b and a inertial axes with only a small contribution along the c-axis, in agreement with ab initio calculations. Using two-color (1 + 1′) resonance-enhanced multiphoton ionization the S1 excited state lifetime is determined as 70 ± 18 ns.

Panter, Sabrina; Illarionov, Boris; Chen, Jing; Bacher, Adelbert; Fischer, Markus; Weber, Stefan

doi: 10.1039/d5cp02105gpmid: 40856789

6,7,8-Trimethyllumazine (TML) is a structural analog of the natural cofactor 6,7-dimethyl-8-ribityllumazine. Under basic conditions, TML undergoes a distinctive disproportionation reaction upon photoexcitation. The transiently formed radical pair can be investigated by photo-chemically induced dynamic nuclear polarization (photo-CIDNP) spectroscopy. In this contribution, the structure of the TML anion is analyzed systematically using NMR spectroscopy. Furthermore, the transiently formed TML radicals are investigated and their hyperfine structures elucidated by 1H and 13C photo-CIDNP spectroscopy. Experimental photo-CIDNP intensities are compared with isotropic hyperfine coupling constants from density functional theory (DFT) calculations. The results confirm the formation of an oxidized TML˙ radical and a reduced TMLH˙− radical, the latter potentially protonated at N1. Comparative analysis reveals a substantially different hyperfine structure of the formed radical species which is rationalized based on calculations of spin density distributions. The results provide important insights into photo-induced one-electron transfer reactions of 6,7-dimethyllumazines and their potential role in redox processes in biological systems. The detection and characterization of the oxidized TML˙ radical is of special interest as this oxidation state has not been satisfactorily described in the literature so far. Thus this contribution advances the understanding of the mechanism of formation and the structure of lumazine radicals.